Method of light stabilizing a colorant

ABSTRACT

A light-stable colored composition which includes a colorant and a radiation transorber. The colorant, in the presence of the radiation transorber, is adapted, upon exposure of the transorber to specific, narrow bandwidth radiation, to be mutable. The radiation transorber also imparts light-stability to the colorant so that the colorant does not fade when exposed to sunlight or artificial light.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This patent application is a continuation-in-part patent application ofU.S. patent application Ser. No. 08/403,240, filed on Mar. 10, 1995, nowabandoned, which is a continuation-in-part of U.S. patent applicationSer. No. 08/373,958, filed on Jan. 17, 1995, now abandoned, which is acontinuation-in-part of U.S. patent application Ser. No. 08/360,501,pending filed on Dec. 21, 1994, and a continuation-in-part of U.S.patent application Ser. No. 08/359,670, filed on Dec. 20, 1994, nowabandoned, both of which are continuation-in-part patent applications ofU.S. patent application Ser. No. 08/258,858, filed on Jun. 13, 1994, nowabandoned, which is a continuation-in-part patent application of U.S.patent application Ser. No. 08/119,912, filed Sep. 10, 1993, nowabandoned, which is a continuation-in-part patent application of U.S.patent application Ser. No. 08/103,503, filed on Aug. 5, 1993, nowabandoned, all of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a family of colorants and colorantmodifiers. The colorant modifiers, according to the present invention,are capable of stabilizing a color to ordinary light and/or renderingthe colorant mutable when exposed to specific wavelengths ofelectromagnetic radiation.

BACKGROUND OF THE INVENTION

A major problem with colorants is that they tend to fade when exposed tosunlight or artificial light. It is believed that most of the fading ofcolorants when exposed to light is due to photodegradation mechanisms.These degradation mechanisms include oxidation or reduction of thecolorants depending upon the environmental conditions in which thecolorant is placed. Fading of a colorant also depends upon the substrateupon which they reside.

Product analysis of stable photoproducts and intermediates has revealedseveral important modes of photodecomposition. These include electronejection from the colorant, reaction with ground-state or excitedsinglet state oxygen, cleavage of the central carbon-phenyl ring bondsto form amino substituted benzophenones, such as triphenylmethane dyes,reduction to form the colorless leuco dyes and electron or hydrogen atomabstraction to form radical intermediates.

Various factors such as temperature, humidity, gaseous reactants,including O₂, O₃, SO₂, and NO₂, and water soluble, nonvolatilephotodegradation products have been shown to influence fading ofcolorants. The factors that effect colorant fading appear to exhibit acertain amount of interdependence. It is due to this complex behaviorthat observations for the fading of a particular colorant on aparticular substrate cannot be applied to colorants and substrates ingeneral.

Under conditions of constant temperature it has been observed that anincrease in the relative humidity of the atmosphere increases the fadingof a colorant for a variety of colorant-substrate systems (e.g.,McLaren, K., J. Soc. Dyers Colour, 1956, 72, 527). For example, as therelative humidity of the atmosphere increases, a fiber may swell becausethe moisture content of the fiber increases. This aids diffusion ofgaseous reactants through the substrate structure.

The ability of a light source to cause photochemical change in acolorant is also dependent upon the spectral distribution of the lightsource, in particular the proportion of radiation of wavelengths mosteffective in causing a change in the colorant and the quantum yield ofcolorant degradation as a function of wavelength. On the basis ofphotochemical principles, it would be expected that light of higherenergy (short wavelengths) would be more effective at causing fadingthan light of lower energy (long wavelengths). Studies have revealedthat this is not always the case. Over 100 colorants of differentclasses were studied and found that generally the most unstable werefaded more efficiently by visible light while those of higherlightfastness were degraded mainly by ultraviolet light (McLaren, K., J.Soc. Dyers Colour, 1956, 72, 86).

The influence of a substrate on colorant stability can be extremelyimportant. Colorant fading may be retarded or promoted by some chemicalgroup within the substrate. Such a group can be a ground-state speciesor an excited-state species. The porosity of the substrate is also animportant factor in colorant stability. A high porosity can promotefading of a colorant by facilitating penetration of moisture and gaseousreactants into the substrate. A substrate may also act as a protectiveagent by screening the colorant from light of wavelengths capable ofcausing degradation.

The purity of the substrate is also an important consideration wheneverthe photochemistry of dyed technical polymers is considered. Forexample, technical-grade cotton, viscose rayon, polyethylene,polypropylene, and polyisoprene are known to contain carbonyl groupimpurities. These impurities absorb light of wavelengths greater than300 nm, which are present in sunlight, and so, excitation of theseimpurities may lead to reactive species capable of causing colorantfading (van Beek, H.C.A., Col. Res. Appl., 1983, 8(3), 176).

Therefore, there exists a great need for methods and compositions whichare capable of stabilizing a wide variety of colorants from the effectsof both sunlight and artificial light.

There is also a need for colorants that can be mutated, preferably froma colored to a colorless form, when exposed to a specific predeterminedwavelength of electromagnetic radiation. For certain uses, the idealcolorant would be one that is stable in ordinary light and can bemutated to a colorless form when exposed to a specific predeterminedwavelength of electromagnetic radiation.

SUMMARY OF THE INVENTION

The present invention addresses the needs described above by providingcompositions and methods for stabilizing colorants against radiationincluding radiation in the visible wavelength range. In addition, thepresent invention provides certain embodiments in which the light-stablecolorant system is mutable by exposure to certain narrow bandwidths ofradiation. In certain embodiments, the colorant system is stable inordinary visible light and is mutable when exposed to a specificwavelength of electromagnetic radiation.

In one embodiment, the present invention provides a compositioncomprising a colorant which, in the presence of a radiation transorber,is mutable when exposed to a specific wavelength of radiation, while atthe same time, provides light stability to the colorant when thecomposition is exposed to sunlight or artificial light. The radiationtransorber may be any material which is adapted to absorb radiation andinteract with the colorant to effect the mutation of the colorant.Generally, the radiation transorber contains a photoreactor and awavelength-specific sensitizer. The wavelength-specific sensitizergenerally absorbs radiation having a specific wavelength, and thereforea specific amount of energy, and transfers the energy to thephotoreactor. It is desirable that the mutation of the colorant beirreversible.

The present invention also relates to colorant compositions havingimproved stability, wherein the colorant is associated with a modifiedphotoreactor. It has been determined that conventional photoreactors,which normally contain a carbonyl group with a functional group on thecarbon alpha to the carbonyl group, acquire the ability to stabilizecolorants when the functional group on the alpha carbon is removed viadehydration.

Accordingly, the present invention also includes a novel method ofdehydrating photoreactors that have a hydroxyl group in the alphaposition to a carbonyl group. This reaction is necessary to impart thecolorant stabilizing capability to the photoreactor. The novel method ofdehydrating photoreactors that have a hydroxyl group in the alphaposition to a carbonyl group can be used with a wide variety ofphotoreactors to provide the colorant stabilizing capability to thephotoreactor. The resulting modified photoreactor can optionally belinked to wavelength-selective sensitizer to impart the capability ofdecolorizing a colorant when exposed to a predetermined narrowwavelength of electromagnetic radiation. Accordingly, the presentinvention provides a photoreactor capable of stabilizing a colorant thatit is admixed with.

In certain embodiments of the present invention, the mixture of colorantand radiation transorber is mutable upon exposure to radiation. In thisembodiment, the photoreactor may or may not be modified as describedabove to impart stability when admixed to a colorant. In one embodiment,an ultraviolet radiation transorber is adapted to absorb ultravioletradiation and interact with the colorant to effect the irreversiblemutation of the colorant. It is desirable that the ultraviolet radiationtransorber absorb ultraviolet radiation at a wavelength of from about 4to about 300 nanometers. It is even more desirable that the ultravioletradiation transorber absorb ultraviolet radiation at a wavelength of 100to 300 nanometers. The colorant in combination with the ultravioletradiation transorber remains stable when exposed to sunlight orartificial light. If the photoreactor is modified as described above,the colorant has improved stability when exposed to sunlight orartificial light.

Another stabilizer that is considered part of the present invention isan arylketoalkene having the following general formula: ##STR1## whereinR₁ is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl ora heteroaryl group;

R₂ is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or aheteroaryl group;

R₃ is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or aheteroaryl group; and

R₄ is an aryl, heteroaryl, or substituted aryl group.

Preferably, the alkene group is in the trans configuration.

Desirably, the arylketoalkene stabilizing compound has the followingformula. ##STR2## which efficiently absorbs radiation having awavelength at about 308 nanometers, or ##STR3## which efficientlyabsorbs radiation having a wavelength at about 280 nanometers.Desirably, arylketoalkene stabilizing compound of the present inventionis in the trans configuration with respect to the double bond. However,the sensitizer may also be in the cis configuration across the doublebond.

Accordingly, this embodiment of the present invention provides astabilizing molecule, the above arylketoalkene, which when associatedwith a colorant, stabilizes the colorant. Therefore, the abovearylketoalkene can be used as an additive to any colorant composition.For example, as the arylketoalkene compound is poorly soluble in water,it can be directly added to solvent or oil based (not water based)colorant compositions. Additionally, the arylketoalkene compound can beadded to other colorant compositions that contain additives enabling thesolubilization of the compound therein. Further, the arylketoalkenestabilizing compounds can be solubilized in an aqueous solution byattaching the compound to a large water soluble molecule, such as acyclodextrin.

In another embodiment of the present invention, the colored compositionof the present invention may also contain a molecular includant having achemical structure which defines at least one cavity. The molecularincludants include, but are not limited to, clathrates, zeolites, andcyclodextrins. Each of the colorant and ultraviolet radiation transorberor modified photoreactor or arylketoalkene stabilizing compound can beassociated with one or more molecular includant. The includant can havemultiple radiation transorbers associated therewith (see co-pending U.S.patent application Ser. No. 08/359,670). In other embodiments, theincludant can have many modified photoreactors or arylketoalkenestabilizing compounds associated therewith.

In some embodiments, the colorant is at least partially included withina cavity of the molecular includant and the ultraviolet radiationtransorber or modified photoreactor or arylketoalkene stabilizer isassociated with the molecular includant outside of the cavity. In someembodiments, the ultraviolet radiation transorber or modifiedphotoreactor or arylketoalkene stabilizer is covalently coupled to theoutside of the molecular includant.

The present invention also relates to a method of mutating the colorantassociated with the composition of the present invention. The methodcomprises irradiating a composition containing a mutable colorant and anultraviolet radiation transorber with ultraviolet radiation at a dosagelevel sufficient to mutate the colorant. As stated above, in someembodiments the composition further includes a molecular includant. Inanother embodiment, the composition is applied to a substrate beforebeing irradiated with ultraviolet radiation. It is desirable that themutated colorant is stable.

The present invention is also related to a substrate having an imagethereon that is formed by the composition of the present invention. Thecolorant, in the presence of the radiation transorber or modifiedphotoreactor or arylketoalkene compound, is more stable to sunlight orartificial light. When a molecular includant is included in thecomposition, the colorant is stabilized by a lower ratio of radiationtransorbers to colorant.

The present invention also includes a dry imaging process wherein theimaging process utilizes, for example, the following three mutablecolorants: cyan, magenta, and yellow. These mutable colorants can belayered on the substrate or can be mixed together and applied as asingle layer. Using, for example, laser technology with three lasers atdifferent wavelengths, an image can be created by selectively "erasing"colorants. A further advantage of the present invention is that theremaining colorants are stable when exposed to ordinary light.

The present invention also includes a method of storing data utilizingthe mutable colorant on a substrate, such as a disc. The colorant isselectively mutated using a laser at the appropriate wavelength toprovide the binary information required for storing the information. Thepresent invention is particularly useful for this purpose because theunmutated colorant is stabilized to ordinary light by the radiationtransorber and can be further stabilized by the optionally includedmolecular includant.

The present invention also includes data processing forms for use withphoto-sensing apparatus that detect the presence of indicia atindicia-receiving locations of the form. The data processing forms arecomposed of a sheet of carrier material and a plurality ofindicia-receiving locations on the surface of the sheet. Theindicia-receiving locations are defined by a colored compositionincluding a mutable colorant and a radiation transorber. The dataprocessing forms of the present invention are disclosed in co-pendingU.S. patent application Ser. No. 08/360,501, which is incorporatedherein by reference.

These and other features and advantages of the present invention willbecome apparent after a review of the following detailed description ofthe disclosed embodiments and the appended claims.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates an ultraviolet radiation transorber/mutablecolorant/molecular includant complex wherein the mutable colorant ismalachite green, the ultraviolet radiation transorber is IRGACURE 184(1-hydroxycyclohexyl phenyl ketone), and the molecular includant isβ-cyclodextrin.

FIG. 2 illustrates an ultraviolet radiation transorber/mutablecolorant/molecular includant complex wherein the mutable colorant isVictoria Pure Blue BO (Basic Blue 7), the ultraviolet radiationtransorber is IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone), and themolecular includant is β-cyclodextrin.

FIG. 3 is a plot of the average number of ultraviolet radiationtransorber molecules which are covalently coupled to each molecule of amolecular includant in several colored compositions, which number alsois referred to by the term, "degree of substitution," versus thedecolorization time upon exposure to 222-nanometer excimer lampultraviolet radiation.

FIG. 4 is an illustration of several 222 nanometer excimer lampsarranged in four parallel columns wherein the twelve numbers representthe locations where twelve intensity measurements were obtainedapproximately 5.5 centimeters from the excimer lamps.

FIG. 5 is an illustration of several 222 nanometer excimer lampsarranged in four parallel columns wherein the nine numbers represent thelocations where nine intensity measurements were obtained approximately5.5 centimeters from the excimer lamps.

FIG. 6 is an illustration of several 222 nanometer excimer lampsarranged in four parallel columns wherein the location of the number "1"denotes the location where ten intensity measurements were obtained fromincreasing distances from the lamps at that location. (The measurementsand their distances from the lamp are summarized in Table 12.)

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates in general to a light-stable colorantsystem that is optionally mutable by exposure to narrow band-widthradiation. The present invention more particularly relates to acomposition comprising a colorant which, in the presence of a radiationtransorber, is stable under ordinary light but is mutable when exposedto specific, narrow band-width radiation. The radiation transorber iscapable of absorbing radiation and interacting with the colorant toeffect a mutation of the colorant. The radiation transorber may be anymaterial which is adapted to absorb radiation and interact with thecolorant to effect the mutation of the colorant. Generally, theradiation transorber contains a photoreactor and a wavelength-specificsensitizer. The wavelength-specific sensitizer generally absorbsradiation having a specific wavelength, and therefore a specific amountof energy, and transfers the energy to the photoreactor. It is desirablethat the mutation of the colorant be irreversible.

The present invention also relates to colorant compositions havingimproved stability, wherein the colorant is associated with a modifiedphotoreactor. It has been determined that conventional photoreactorswhich normally contain a carbonyl group with a functional group on thecarbon alpha to the carbonyl group acquire the ability to stabilizecolorants when the functional group on the alpha carbon is removed.Accordingly, the present invention also includes a novel method ofdehydrating photoreactors that have a hydroxyl group in the alphaposition to a carbonyl group. This reaction is necessary to impart thecolorant stabilizing capability to the photoreactor. The novel method ofdehydrating photoreactors that have a hydroxyl group in the alphaposition to a carbonyl group can be used with a wide variety ofphotoreactors to provide the colorant stabilizing capability to thephotoreactor. The resulting modified photoreactor can optionally belinked to a wavelength-selective sensitizer to impart the capability ofdecolorizing a colorant when exposed to a predetermined narrowwavelength of electromagnetic radiation. Accordingly, the presentinvention provides a photoreactor capable of stabilizing a colorant withwhich it is admixed.

In certain embodiments of the present invention, the colorant andradiation transorber is mutable upon exposure to radiation. In thisembodiment, the photoreactor may or may not be modified as describedabove to impart stability when admixed to a colorant. In one embodiment,an ultraviolet radiation transorber is adapted to absorb ultravioletradiation and interact with the colorant to effect the irreversiblemutation of the colorant. It is desirable that the ultraviolet radiationtransorber absorb ultraviolet radiation at a wavelength of from about 4to about 300 nanometers. If the photoreactor in the radiation transorberis modified as described above, the colorant has improved stability whenexposed to sunlight or artificial light.

The present invention also relates to a method of mutating the colorantin the composition of the present invention. The method comprisesirradiating a composition containing a mutable colorant and a radiationtransorber with radiation at a dosage level sufficient to mutate thecolorant.

The present invention further relates to a method of stabilizing acolorant comprising associating the modified photoreactor describedabove with the colorant. Optionally, the photoreactor may be associatedwith a wavelength-selective sensitizer, or the photoreactor may beassociated with a molecular includant, or both.

Thus, the stabilizing compound produced by the process of dehydrating atertiary alcohol group that is alpha to a carbonyl group on aphotoreactor is shown in the following general formula: ##STR4## whereinR₁ is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl ora heteroaryl group;

R₂ is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or aheteroaryl group;

R₃ is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or aheteroaryl group; and

R₄ is an aryl, heteroaryl, or substituted aryl group.

Preferably, the alkene group is in the trans configuration.

Desirably, the arylketoalkene stabilizing compound is represented by thefollowing formulas: ##STR5##

Accordingly, this embodiment of the present invention provides astabilizing molecule, the above arylketoalkene, which when associatedwith a colorant, stabilizes the colorant. Therefore, the abovearylketoalkene can be used as an additive to any colorant composition.For example, as the arylketoalkene compound is not water soluble, it canbe directly added to solvent or oil based (not water based) colorantcompositions. Additionally, the arylketoalkene compound can be added toother colorant compositions that contain additives enabling thesolubilization of the compound therein. Further, the arylketoalkenestabilizing compounds can be solubilized in an aqueous solution byattaching the compound to a large water soluble molecule, such as acyclodextrin.

After definitions of various terms used herein, the mutable colorantcomposition of the present invention and methods for making and usingthat composition are described in detail, followed by a detaileddescription of the improved light stable composition of the presentinvention and methods for making the improved light stable compositions.

Definitions

The term "composition" and such variations as "colored composition" areused herein to mean a colorant, and a radiation transorber or a modifiedphotoreactor or an arylketoalkene stabilizer. Where the coloredcomposition includes the modified photoreactor, it may further comprisea wavelength-selective sensitizer. Where the colored compositionincludes the arylketoalkene stabilizer, it may further comprise aphotoreactor. When reference is being made to a colored compositionwhich is adapted for a specific application, the term"composition-based" is used as a modifier to indicate that the materialincludes a colorant, an ultraviolet radiation transorber or a modifiedphotoreactor or an arylketoalkene stabilizer, and, optionally, amolecular includant.

As used herein, the term "colorant" is meant to include, withoutlimitation, any material which typically will be an organic material,such as an organic colorant or pigment. Desirably, the colorant will besubstantially transparent to, that is, will not significantly interactwith, the ultraviolet radiation to which it is exposed. The term ismeant to include a single material or a mixture of two or morematerials.

As used herein, the term "irreversible" means that the colorant will notrevert to its original color when it no longer is exposed to ultravioletradiation.

The term "radiation transorber" is used herein to mean any materialwhich is adapted to absorb radiation at a specific wavelength andinteract with the colorant to affect the mutation of the colorant and,at the same time, protect the colorant from fading in sunlight orartificial light. The term "ultraviolet radiation transorber" is usedherein to mean any material which is adapted to absorb ultravioletradiation and interact with the colorant to effect the mutation of thecolorant. In some embodiments, the ultraviolet radiation transorber maybe an organic compound. Where the radiation transorber is comprised of awavelength-selective sensitizer and a photoreactor, the photoreactor mayoptionally be modified as described below.

The term "compound" is intended to include a single material or amixture of two or more materials. If two or more materials are employed,it is not necessary that all of them absorb radiation of the samewavelength. As discussed more fully below, a radiation transorber iscomprised of a photoreactor and a wavelength selective sensitizer. Theradiation transorber has the additional property of making the colorantwith which the radiation transorber is associated light stable tosunlight or artificial light.

The term "light-stable" is used herein to mean that the colorant, whenassociated with the radiation transorber or modified photoreactor orarylketoalkene stabilizer molecule, is more stable to light, including,but not limited to, sunlight or artificial light, than when the colorantis not associated with these compounds.

The term "molecular includant," as used herein, is intended to mean anysubstance having a chemical structure which defines at least one cavity.That is, the molecular includant is a cavity-containing structure. Asused herein, the term "cavity" is meant to include any opening or spaceof a size sufficient to accept at least a portion of one or both of thecolorant and the ultraviolet radiation transorber.

The term "functionalized molecular includant" is used herein to mean amolecular includant to which one or more molecules of an ultravioletradiation transorber or modified photoreactor or arylketoalkenestabilizer are covalently coupled to each molecule of the molecularincludant. The term "degree of substitution" is used herein to refer tothe number of these molecules or leaving groups (defined below) whichare covalently coupled to each molecule of the molecular includant.

The term "derivatized molecular includant" is used herein to mean amolecular includant having more than two leaving groups covalentlycoupled to each molecule of molecular includant. The term "leavinggroup" is used herein to mean any leaving group capable of participatingin a bimolecular nucleophilic substitution reaction.

The term "artificial light" is used herein to mean light having arelatively broad bandwidth that is produced from conventional lightsources, including, but not limited to, conventional incandescent lightbulbs and fluorescent light bulbs.

The term "ultraviolet radiation" is used herein to mean electromagneticradiation having wavelengths in the range of from about 4 to about 400nanometers. The especially desirable ultraviolet radiation range for thepresent invention is between approximately 100 to 375 nanometers. Thus,the term includes the regions commonly referred to as ultraviolet andvacuum ultraviolet. The wavelength ranges typically assigned to thesetwo regions are from about 180 to about 400 nanometers and from about100 to about 180 nanometers, respectively.

The term "thereon" is used herein to mean thereon or therein. Forexample, the present invention includes a substrate having a coloredcomposition thereon. According to the definition of "thereon" thecolored composition may be present on the substrate or it may be in thesubstrate.

The term "mutable," with reference to the colorant, is used to mean thatthe absorption maximum of the colorant in the visible region of theelectromagnetic spectrum is capable of being mutated or changed byexposure to radiation, preferably ultraviolet radiation, when in thepresence of the radiation transorber. In general, it is only necessarythat such absorption maximum be mutated to an absorption maximum whichis different from that of the colorant prior to exposure to theultraviolet radiation, and that the mutation be irreversible. Thus, thenew absorption maximum can be within or outside of the visible region ofthe electromagnetic spectrum. In other words, the colorant can mutate toa different color or be rendered colorless. The latter is also desirablewhen the colorant is used in data processing forms for use withphoto-sensing apparatus that detect the presence of indicia atindicia-receiving locations of the form.

Functionalized Molecular Includant

In several embodiments, the radiation transorber molecule, thewavelength-selective sensitizer, the photoreactor, or the arylketoalkenestabilizer may be associated with a molecular includant. It is to benoted that in all the formulas, the number of such molecules can bebetween approximately 1 and approximately 21 molecules per molecularincludant. Of course, in certain situations, there can be more than 21molecules per molecular includant molecule. Desirably, there are morethan three of such molecules per molecular includant.

The degree of substitution of the functionalized molecular includant maybe in a range of from 1 to approximately 21. As another example, thedegree of substitution may be in a range of from 3 to about 10. As afurther example, the degree of substitution may be in a range of fromabout 4 to about 9.

The colorant is associated with the functionalized molecular includant.The term "associated" in its broadest sense means that the colorant isat least in close proximity to the functionalized molecular includant.For example, the colorant may be maintained in close proximity to thefunctionalized molecular includant by hydrogen bonding, van der Waalsforces, or the like. Alternatively, the colorant may be covalentlybonded to the functionalized molecular includant, although this normallyis neither desired nor necessary. As a further example, the colorant maybe at least partially included within the cavity of the functionalizedmolecular includant.

The examples below disclose methods of preparing and associating thesecolorants and ultraviolet radiation transorbers to β-cyclodextrins. Forillustrative purposes only, Examples 1, 2, 6, and 7 disclose one or moremethods of preparing and associating colorants and ultraviolet radiationtransorbers to cyclodextrins.

In those embodiments of the present inveniton in which the ultravioletradiation transorber is covalently coupled to the molecular includant,the efficiency of energy transfer from the ultraviolet radiationtransorber to the colorant is, at least in part, a function of thenumber of ultraviolet radiation transorber molecules which are attachedto the molecular includant. It now is known that the synthetic methodsdescribed above result in covalently coupling an average of twotransorber molecules to each molecule of the molecular includant.Because the time required to mutate the colorant should, at least inpart, be a function of the number of ultraviolet radiation transorbermolecules coupled to each molecule of molecular includant, there is aneed for an improved colored composition in which an average of morethan two ultraviolet radiation transorber molecules are covalentlycoupled to each molecule of the molecular includant.

Accordingly, the present invention also relates to a composition whichincludes a colorant and a functionalized molecular includant. Forillustrative purposes only, Examples 12 through 19, and 21 through 22disclose other methods of preparing and associating colorants andultraviolet radiation transorbers to cyclodextrins, wherein more thantwo molecules of the ultraviolet radiation transorber are covalentlycoupled to each molecule of the molecular includant. Further, Examples29 and 31 disclose methods of preparing and associating arylketoalkenestabilizers with cyclodextrin, wherein the cyclodextrin has an averageof approximately 3 or 4 stabilizer molecules attached thereto.

The present invention also provides a method of making a functionalizedmolecular includant. The method of making a functionalized molecularincludant involves the steps of providing a derivatized ultravioletradiation transorber having a nucleophilic group, providing aderivatized molecular includant having more than two leaving groups permolecule, and reacting the derivatized ultraviolet radiation transorberwith the derivatized molecular includant under conditions sufficient toresult in the covalent coupling of an average of more than twoultraviolet radiation transorber molecules to each molecular includantmolecule. By way of example, the derivatized ultraviolet radiationtransorber may be 2- p-(2-methyl-2-mercaptomethylpropionyl)phenoxy!ethyl1,3-dioxo-2-isoindoline-acetate. As another example, the derivatizedultraviolet radiation transorber may be 2-mercaptomethyl-2-methyl-4'- 2-p-(3-oxobutyl)phenoxy!ethoxy!propiophenone.

In general, the derivatized ultraviolet radiation transorber and thederivatized molecular includant are selected to cause the covalentcoupling of the ultraviolet radiation transorber to the molecularincludant by means of a bimolecular nucleophilic substitution reaction.Consequently, the choice of the nucleophilic group and the leavinggroups and the preparation of the derivatized ultraviolet radiationtransorber and derivatized molecular includant, respectively, may bereadily accomplished by those having ordinary skill in the art withoutthe need for undue experimentation.

The nucleophilic group of the derivatized ultraviolet radiationtransorber may be any nucleophilic group capable of participating in abimolecular nucleophilic substitution reaction, provided, of course,that the reaction results in the covalent coupling of more than twomolecules of the ultraviolet radiation transorber to the molecularincludant. The nucleophilic group generally will be a Lewis base, i.e.,any group having an unshared pair of electrons. The group may be neutralor negatively charged. Examples of nucleophilic groups include, by wayof illustration only, aliphatic hydroxy, aromatic hydroxy, alkoxides,carboxy, carboxylate, amino, and mercapto.

Similarly, the leaving group of the derivatized molecular includant maybe any leaving group capable of participating in a bimolecularnucleophilic substitution reaction, again provided that the reactionresults in the covalent coupling of more than two molecules of theultraviolet radiation transorber to the molecular includant. Examples ofleaving groups include, also by way of illustration only,p-toluenesulfonates (tosylates), p-bromobenzenesulfonates (brosylates),p-nitrobenzenesulfonates (nosylates), methanesulfonates (mesylates),oxonium ions, alkyl perchlorates, ammonioalkane sulfonate esters(betylates), alkyl fluorosuffonates, trifluoromethanesulfonates(triflates), nonafluorobutanesulfonates (nonaflates), and2,2,2-trifluoroethanesulfonates (tresylates).

The reaction of the derivatized ultraviolet radiation transorber withthe derivatized molecular includant is carried out in solution. Thechoice of solvent depends upon the solubilities of the two derivatizedspecies. As a practical matter, a particularly useful solvent isN,N-dimethylformamide (DMF).

The reaction conditions, such as temperature, reaction time, and thelike generally are matters of choice based upon the natures of thenucleophilic and leaving groups. Elevated temperatures usually are notrequired. For example, the reaction temperature may be in a range offrom about 0° C. to around ambient temperature, i.e., to 20°-25° C.

The preparation of the functionalized molecular includant as describedabove generally is carried out in the absence of the colorant. However,the colorant may be associated with the derivatized molecular includantbefore reacting the derivatized ultraviolet radiation transorber withthe derivatized molecular includant, particularly if a degree ofsubstitution greater than about three is desired. When the degree ofsubstitution is about three, it is believed that the association of thecolorant with the functionalized molecular includant still may permitthe colorant to be at least partially included in a cavity of thefunctionalized molecular includant. At higher degrees of substitution,such as about six, steric hindrance may partially or completely preventthe colorant from being at least partially included in a cavity of thefunctionalized molecular includant. Consequently, the colorant may beassociated with the derivatized molecular includant which normally willexhibit little, if any, steric hindrance. In this instance, the colorantwill be at least partially included in a cavity of the derivatizedmolecular includant. The above-described bimolecular nucleophilicsubstitution reaction then may be carried out to give a coloredcomposition of the present invention in which the colorant is at leastpartially included in a cavity of the functionalized molecularincludant.

Mutable Compositions

As stated above, the present invention provides compositions comprisinga colorant which, in the presence of a radiation transorber, is mutablewhen exposed to a specific wavelength of radiation, while at the sametime, provides light stability to the colorant with respect to sunlightand artificial light. Desirably, the mutated colorant will be stable,i.e., not appreciably adversely affected by radiation normallyencountered in the environment, such as natural or artificial light andheat. Thus, desirably, a colorant rendered colorless will remaincolorless indefinitely.

The dye, for example, may be an organic dye. Organic dye classesinclude, by way of illustration only, triarylmethyl dyes, such asMalachite Green Carbinol base {4-(dimethylamino)-α-4-(dimethylamino)phenyl!-α-phenylbenzene-methanol}, Malachite GreenCarbinol hydrochloride {N-4-4-(dimethylamino)phenyl!phenylmethylene!-2,5-cyclohexyldien-1-ylidene!-N-methyl-methanaminiumchloride or bis p-(dimethylamino)phenyl!phenylmethylium chloride}, andMalachite Green oxalate {N-4-4-(dimethylamino)phenyl!phenylmethylene!-2,5-cyclohexyldien-1-ylidene!-N-methylmethanaminiumchloride or bis p-(dimethylamino)phenyl!phenylmethylium oxalate};monoazo dyes, such as Cyanine Black, Chrysoidine Basic Orange 2;4-(phenylazo)-1,3-benzenediamine monohydrochloride!, Victoria Pure BlueBO, Victoria Pure Blue B, basic fuschin and β-Naphthol Orange; thiazinedyes, such as Methylene Green, zinc chloride double salt3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloridedouble salt!; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine);naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2-(hydrazinocarbonyl)amino!-2,3-dihydro-1,3-dioxo-1H-benzde!isoquinoline-5,8-disulfonic acid dilithium salt }; azine dyes, suchas Janus Green B {3-(diethylamino)-7-4-(dimethylamino)phenyl!azo!-5-phenylphenazinium chloride}; cyaninedyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2- 7-1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benze!indol-2-ylidene!-1,3,5-heptatrienyl!-1,1-dimethyl-3-(4-sulfobutyl)-1H-benze!indolium hydroxide inner salt sodium salt}; indigo dyes, such asIndigo {Indigo Blue or Vat Blue 1;2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-3-one};coumarin dyes, such as 7-hydroxy-4-methylcoumarin(4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258bisbenzimide or2-(4-hydroxyphenyl)-5-(4-methyl-1-pipera-zinyl)-2,5-bi-1H-benzimidazoletrihydrochloride pentahydrate!; paraquinoidal dyes, such as Hematoxylin{Natural Black 1; 7,11b-dihydrobenz b!indeno1,2-d!pyran-3,4,6a,9,10(6H)-pentol}; fluorescein dyes, such asFluoresceinamine (5-aminofluorescein); diazonium salt dyes, such asDiazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt;2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt);azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20;4-benzoylamino-2,5-diethoxybenzene diazonium chloride, zinc chloridedouble salt); phenylenediamine dyes, such as Disperse Yellow 9N-(2,4-dinitrophenyl)-1,4-phenylenediamine or Solvent Orange 53!; diazodyes, such as Disperse Orange 13 Solvent Orange 52;1-phenylazo-4-(4-hydroxyphenylazo)naphthalene!; anthraquinone dyes, suchas Disperse Blue 3 Celliton Fast Blue FFR;1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone!, Disperse Blue14 Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone!, andAlizarin Blue Black B (Mordant Black 13); trisazo dyes, such as DirectBlue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3- (4- (4-(6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo!-6-sulfo-1-naphthalenyl)azo!-1-naphthalenyl)azo!-1,5-naphthalenedisulfonicacid tetrasodium salt}; xanthene dyes, such as 2,7-dichlorofluorescein;proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine);sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein);phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15;(SP-4-1)- 29H,31H-phthalocyanato(2-)-N²⁹,N³⁰,N³¹,N³² !copper};carotenoid dyes, such as trans-β-carotene (Food Orange 5); carminic aciddyes, such as Carmine, the aluminum or calcium-aluminum lake of carminicacid(7-a-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-2-anthracenecarbonylicacid); azure dyes, such as Azure A3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or7-(dimethylamino)-3-imino-3H-phenothiazine hydrochloride!; and acridinedyes, such as Acridine Orange Basic Orange 14;3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt!and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridiniumchloride mixture with 3,6-acridinediamine).

The present invention includes unique compounds, namely, radiationtransorbers, that are capable of absorbing narrow ultraviolet wavelengthradiation, while at the same time, imparting light-stability to acolorant with which the compounds are associated. The compounds aresynthesized by combining a wavelength-selective sensitizer and aphotoreactor. The photoreactors oftentimes do not efficiently absorbhigh energy radiation. When combined with the wavelength-selectivesensitizer, the resulting compound is a wavelength specific compoundthat efficiently absorbs a very narrow spectrum of radiation. Thewavelength-selective sensitizer may be covalently coupled to thephotoreactor.

By way of example, the wavelength-selective sensitizer may be selectedfrom the group consisting of phthaloylglycine and4-(4-oxyphenyl)-2-butanone. As another example, the photoreactor may beselected from the group consisting of 1-4-(2-hydroxyethoxy)phenyl!-2-hydroxy-2-methylpropan-1-one andcyclohexyl-phenyl ketone ester. Other photoreactors are listed by way ofexample, in the detailed description below regarding the impovedstabilized composition of the present invention. As a further example,the ultraviolet radiation transorber may be 2-p-2-methyllactoyl)phenoxy!ethyl 1,3-dioxo-2-isoin-dolineacetate. Asstill another example, the ultraviolet radiation transorber may be2-hydroxy-2-methyl-4'-2- p-(3-oxobutyl)phenoxy!propiophenone.

Although the colorant and the ultraviolet radiation transorber have beendescribed as separate compounds, they can be part of the same molecule.For example, they can be covalently coupled to each other, eitherdirectly, or indirectly through a relatively small molecule, or spacer.Alternatively, the colorant and ultraviolet radiation transorber can becovalently coupled to a large molecule, such as an oligomer or apolymer. Further, the colorant and ultraviolet radiation transorber maybe associated with a large molecule by van der Waals forces, andhydrogen bonding, among other means. Other variations will be readilyapparent to those having ordinary skill in the art.

For example, in an embodiment of the composition of the presentinvention, the composition further comprises a molecular includant.Thus, the cavity in the molecular includant can be a tunnel through themolecular includant or a cave-like space or a dented-in space in themolecular includant. The cavity can be isolated or independent, orconnected to one or more other cavities.

The molecular includant can be inorganic or organic in nature. Incertain embodiments, the chemical structure of the molecular includantis adapted to form a molecular inclusion complex. Examples of molecularincludants are, by way of illustration only, clathrates or intercalates,zeolites, and cyclodextrins. Examples of cyclodextrins include, but arenot limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin,hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, sulfatedβ-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl αcyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γcyclodextrin, octyl succinated α cyclodextrin, octyl succinated βcyclodextrin, octyl succinated γ cyclodextrin and sulfated β andγ-cyclodextrin (American Maize-Products Company, Hammond, Ind.).

The desired molecular includant is α-cyclodextrin. More particularly, insome embodiments, the molecular includant is an α-cyclodextrin. In otherembodiments, the molecular includant is a β-cyclodextrin. Although notwanting to be bound by the following theory, it is believed that thecloser the transorber molecule is to the mutable colorant on themolecular includant, the more efficient the interaction with thecolorant to effect mutation of the colorant. Thus, the molecularincludant with functional groups that can react with and bind thetransorber molecule and that are close to the binding site of themutable colorant are the more desirable molecular includants.

In some embodiments, the colorant and the ultraviolet radiationtransorber are associated with the molecular includant. The term"associated", in its broadest sense, means that the colorant and theultraviolet radiation transorber are at least in close proximity to themolecular includant. For example, the colorant and/or the ultravioletradiation transorber can be maintained in close proximity to themolecular includant by hydrogen bonding, van der Waals forces, or thelike. Alternatively, either or both of the colorant and the ultravioletradiation transorber can be covalently bonded to the molecularincludant. In certain embodiments, the colorant will be associated withthe molecular includant by means of hydrogen bonding and/or van derWaals forces or the like, while the ultraviolet radiation transorber iscovalently bonded to the molecular includant. In other embodiments, thecolorant is at least partially included within the cavity of themolecular includant, and the ultraviolet radiation transorber is locatedoutside of the cavity of the molecular includant.

In one embodiment wherein the colorant and the ultraviolet radiationtransorber are associated with the molecular includant, the colorant iscrystal violet, the ultraviolet radiation transorber is a dehydratedphthaloylglycine-DAROCUR 2959, and the molecular includant isβ-cyclodextrin. In yet another embodiment wherein the colorant and theultraviolet radiation transorber are associated with the molecularincludant, the colorant is crystal violet, the ultraviolet radiationtransorber is 4(4-hydroxyphenyl) butan-2-one-DAROCUR 2959 (chlorosubstituted), and the molecular includant is β-cyclodextrin.

In another embodiment wherein the colorant and the ultraviolet radiationtransorber are associated with the molecular includant, the colorant ismalachite green, the ultraviolet radiation transorber is IRGACURE 184,and the molecular includant is β-cyclodextrin as shown in FIG. 1. Instill another embodiment wherein the colorant and the ultravioletradiation transorber are associated with the molecular includant, thecolorant is Victoria Pure Blue BO, the ultraviolet radiation transorberis IRGACURE 184, and the molecular includant is β-cyclodextrin as shownin FIG. 2.

The present invention also relates to a method of mutating the colorantin the composition of the present invention. Briefly described, themethod comprises irradiating a composition containing a mutable colorantand a radiation transorber with radiation at a dosage level sufficientto mutate the colorant. As stated above, in one embodiment thecomposition further includes a molecular includant. In anotherembodiment, the composition is applied to a substrate before beingirradiated with ultraviolet radiation. The composition of the presentinvention may be irradiated with radiation having a wavelength ofbetween about 4 to about 1,000 nanometers. The radiation to which thecomposition of the present invention is exposed generally will have awavelength of from about 4 to about 1,000 nanometers. Thus, theradiation may be ultraviolet radiation, including near ultraviolet andfar or vacuum ultraviolet radiation; visible radiation; and nearinfrared radiation. Desirably, the composition is irradiated withradiation having a wavelength of from about 4 to about 700 nanometers.More desirably, the composition of the present invention is irradiatedwith ultraviolet radiation having a wavelength of from about 4 to about400 nanometers. It is more desirable that the radiation has a wavelengthof between about 100 to 375 nanometers.

Especially desirable radiation is incoherent, pulsed ultravioletradiation produced by a dielectric barrier discharge lamp. Even morepreferably, the dielectric barrier discharge lamp produces radiationhaving a narrow bandwidth, i.e., the half width is of the order ofapproximately 5 to 100 nanometers. Desirably, the radiation will have ahalf width of the order of approximately 5 to 50 nanometers, and moredesirably will have a half width of the order of 5 to 25 nanometers.Most desirably, the half width will be of the order of approximately 5to 15 nanometers.

The amount or dosage level of ultraviolet radiation that the colorant ofthe present invention is exposed to will generally be that amount whichis necessary to mutate the colorant. The amount of ultraviolet radiationnecessary to mutate the colorant can be determined by one of ordinaryskill in the art using routine experimentation. Power density is themeasure of the amount of radiated electromagnetic power traversing aunit area and is usually expressed in watts per centimeter squared(W/cm²). The power density level range is between approximately 5 mW/cm²and 15 mW/cm², more particularly 8 to 10 mW/cm². The dosage level, inturn, typically is a function of the time of exposure and the intensityor flux of the radiation source which irradiates the coloredcomposition. The latter is affected by the distance of the compositionfrom the source and, depending upon the wavelength range of theultraviolet radiation, can be affected by the atmosphere between theradiation source and the composition. Accordingly, in some instances itmay be appropriate to expose the composition to the radiation in acontrolled atmosphere or in a vacuum, although in general neitherapproach is desired.

With regard to the mutation properties of the present invention,photochemical processes involve the absorption of light quanta, orphotons, by a molecule, e.g., the ultraviolet radiation transorber, toproduce a highly reactive electronically excited state. However, thephoton energy, which is proportional to the wavelength of the radiation,cannot be absorbed by the molecule unless it matches the energydifference between the unexcited, or original, state and an excitedstate. Consequently, while the wavelength range of the ultravioletradiation to which the colored composition is exposed is not directly ofconcern, at least a portion of the radiation must have wavelengths whichwill provide the necessary energy to raise the ultraviolet radiationtransorber to an energy level which is capable of interacting with thecolorant.

It follows, then, that the absorption maximum of the ultravioletradiation transorber ideally will be matched with the wavelength rangeof the ultraviolet radiation to increase the efficiency of the mutationof the colorant. Such efficiency also will be increased if thewavelength range of the ultraviolet radiation is relatively narrow, withthe maximum of the ultraviolet radiation transorber coming within suchrange. For these reasons, especially suitable ultraviolet radiation hasa wavelength of from about 100 to about 375 nanometers. Ultravioletradiation within this range desirably may be incoherent, pulsedultraviolet radiation from a dielectric barrier discharge excimer lamp.

The term "incoherent, pulsed ultraviolet radiation" has reference to theradiation produced by a dielectric barrier discharge excimer lamp(referred to hereinafter as "excimer lamp"). Such a lamp is described,for example, by U. Kogelschatz, "Silent discharges for the generation ofultraviolet and vacuum ultraviolet excimer radiation," Pure & Appl.Chem., 62, No. 9, pp. 1667-1674 (1990); and E. Eliasson and U.Kogelschatz, "UV Excimer Radiation from Dielectric-Barrier Discharges,"Appl. Phys. B, 46, pp. 299-303 (1988). Excimer lamps were developedoriginally by ABB Infocom Ltd., Lenzburg, Switzerland. The excimer lamptechnology since has been acquired by Haraus Noblelight AG, Hanau,Germany.

The excimer lamp emits radiation having a very narrow bandwidth, i.e.,radiation in which the half width is of the order of 5-15 nanometers.This emitted radiation is incoherent and pulsed, the frequency of thepulses being dependent upon the frequency of the alternating currentpower supply which typically is in the range of from about 20 to about300 kHz. An excimer lamp typically is identified or referred to by thewavelength at which the maximum intensity of the radiation occurs, whichconvention is followed throughout this specification. Thus, incomparison with most other commercially useful sources of ultravioletradiation which typically emit over the entire ultraviolet spectrum andeven into the visible region, excimer lamp radiation is substantiallymonochromatic.

Excimers are unstable molecular complexes which occur only under extremeconditions, such as those temporarily existing in special types of gasdischarge. Typical examples are the molecular bonds between two raregaseous atoms or between a rare gas atom and a halogen atom. Excimercomplexes dissociate within less than a microsecond and, while they aredissociating, release their binding energy in the form of ultravioletradiation. Known excimers, in general, emit in the range of from about125 to about 360 nanometers, depending upon the excimer gas mixture.

For example, in one embodiment, the colorant of the present invention ismutated by exposure to 222 nanometer excimer lamps. More particularly,the colorant crystal violet is mutated by exposure to 222 nanometerlamps. Even more particularly, the colorant crystal violet is mutated byexposure to 222 nanometer excimer lamps located approximately 5 to 6centimeters from the colorant, wherein the lamps are arranged in fourparallel columns approximately 30 centimeters long. It is to beunderstood that the arrangement of the lamps is not critical to thisaspect of the invention. Accordingly, one or more lamps may be arrangedin any configuration and at any distance which results in the colorantmutating upon exposure to the lamp's ultraviolet radiation. One ofordinary skill in the art would be able to determine by routineexperimentation which configurations and which distances areappropriate. Also, it is to be understood that different excimer lampsare to be used with different ultraviolet radiation transorbers. Theexcimer lamp used to mutate a colorant associated with an ultravioletradiation transorber should produce ultraviolet radiation of awavelength that is absorbed by the ultraviolet radiation transorber.

In some embodiments, the molar ratio of ultraviolet radiation transorberto colorant generally will be equal to or greater than about 0.5. As ageneral rule, the more efficient the ultraviolet radiation transorber isin absorbing the ultraviolet radiation and interacting with, i.e.,transferring absorbed energy to, the colorant to effect irreversiblemutation of the colorant, the lower such ratio can be. Current theoriesof molecular photo chemistry suggest that the lower limit to such ratiois 0.5, based on the generation of two free radicals per photon. As apractical matter, however, ratios higher than 1 are likely to berequired, perhaps as high as about 10. However, the present invention isnot bound by any specific molar ratio range. The important feature isthat the transorber is present in an amount sufficient to effectmutation of the colorant.

While the mechanism of the interaction of the ultraviolet radiationtransorber with the colorant is not totally understood, it is believedthat it may interact with the colorant in a variety of ways. Forexample, the ultraviolet radiation transorber, upon absorbingultraviolet radiation, may be converted to one or more free radicalswhich interact with the colorant. Such free radical-generating compoundstypically are hindered ketones, some examples of which include, but arenot limited to: benzildimethyl ketal (available commercially as IRGACURE651, Ciba-Geigy Corporation, Hawthorne, New York); 1-hydroxycyclohexylphenyl ketone (IRGACURE 500); 2-methyl-1-4-(methylthio)phenyl!-2-morpholino-propan-1-one! (IRGACURE 907);2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (IRGACURE369); and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184).

Alternatively, the ultraviolet radiation may initiate an electrontransfer or reduction-oxidation reaction between the ultravioletradiation transorber and the colorant. In this case, the ultravioletradiation transorber may be, but is not limited to, Michler's ketone(p-dimethylaminophenyl ketone) or benzyl trimethyl stannate. Or, acationic mechanism may be involved, in which case the ultravioletradiation transorber can be, for example, bis4-(diphenylsulphonio)phenyl)! sulfide bis(hexafluorophosphate) (DEGACUREK185, Ciba-Geigy Corporation, Hawthorne, N.Y.); CYRACURE UVI-6990(Ciba-Geigy Corporation), which is a mixture of bis4-(diphenylsulphonio)phenyl! sulfide bis(hexafluorophosphate) withrelated monosulphonium hexafluorophosphate salts; andn5-2,4-(cyclopentadienyl) 1,2,3,4,5,6-n-(methylethyl)benzene!-iron(II)hexafluorophosphate (IRGACURE 261).

Stabilizing Compositions

With regard to the light stabilizing activity of the present invention,it has been determined that in some embodiments it is necessary tomodify a conventional photoreactor to produce the improved light stablecomposition of the present invention. The simplest form of the improvedlight stable composition of the present invention includes a colorantadmixed with a photoreactor modified as described below. The modifiedphotoreactor may or may not be combined with a wavelength-selectivesensitizer. Many conventional photoreactor molecules have a functionalgroup that is alpha to a carbonyl group. The functional group includes,but is not limited to, hydroxyl groups, ether groups, ketone groups, andphenyl groups.

For example, a preferred radiation transorber that can be used in thepresent invention is designated phthaloylglycine-DAROCUR 2959 and isrepresented by the following formula: ##STR6##

The photoreactor portion of the ultraviolet radiation transorber has ahydroxyl group (shaded portion) alpha to the carbonyl carbon. The abovemolecule does not light-stabilize a colorant. However, the hydroxylgroup can be removed by dehydration (see Example 4 and 5) yielding thefollowing compound: ##STR7## This dehydrated phthaloylglycine-DAROCUR2959 is capable of light-stabilizing a colorant. Thus, it is believedthat removal of the functional group alpha to the carbonyl carbon on anyphotoreactor molecule will impart the light-stabilizing capability tothe molecule. While the dehydrated ultraviolet radiation transorber canimpart light-stability to a colorant simply by mixing the molecule withthe colorant, it has been found that the molecule is much more efficientat stabilizing colorants when it is attached to an includant, such ascyclodextrin, as described herein.

It is to be understood that stabilization of a colorant can beaccomplished according to the present invention by utilizing only themodified photoreactor. In other words, a modified photoreactor without awavelength selective sensitizer may be used to stabilize a colorant. Anexample of a photoreactor that is modified according to the presentinvention is DAROCUR 2959. The unmodified DAROCUR 2959 and thedehydrated DAROCUR 2959 are shown below. ##STR8## Other photoreactorscan be modified according to the present invention to providestabilizers for dyes. These photoreactors include, but are not limitedto: 1-Hydroxy-cyclohexyl-phenyl ketone ("HCPK") (IRGACURE 184,Ciba-Geigy); α,α-dimethoxy-α-hydroxy acetophenone (DAROCUR 1173, Merck);1-(4-Isopropylphenyl)-2-hydroxy-2-methyl-propan-1-one (DAROCUR 1116,Merck); 1- 4-(2-Hydroxyethoxy)phenyl!-2-hydroxy-2-methyl-propan-1-one(DAROCUR 2959, Merck); Poly 2-hydroxy-2-methyl-1-4-(1-methylvinyl)phenyl! propan-1-one! (ESACURE KIP, Fratelli Lamberti);Benzoin (2-Hydroxy-1,2-diphenylethanone) (ESACURE BO, FratelliLamberti); Benzoin ethyl ether (2-Ethoxy-1,2-diphenylethanone)(DAITOCURE EE, Siber Hegner); Benzoin isopropyl ether(2-Isopropoxy-1,2-diphenylethanone) (VICURE 30, Stauffer); Benzoinn-butyl ether (2-Butoxy-1,2-diphenylethanone) (ESACURE EB1, FratelliLamberti); mixture of benzoin butyl ethers (TRIGONAL 14, Akzo); Benzoiniso-butyl ether (2-Isobutoxy-1,2-diphenylethanone) (VICURE 10,Stauffer); blend of benzoin n-butyl ether and benzoin isobutyl ether(ESACURE EB3, ESACURE EB4, Fratelli Lamberti); Benzildimethyl ketal(2,2-Dimethoxy-1,2-diphenylethanone) ("BDK") (IRGACURE 651, Ciba-Geigy);2,2-Diethoxy-1,2-diphenylethanone (UVATONE 8302, Upjohn);α,α-Diethoxyacetophenone (2,2-Diethoxy-1-phenyl-ethanone) ("DEAP",Upjohn), (DEAP, Rahn); and α,α-Di-(n-butoxy)-acetophenone(2,2-Dibutoxyl-1-phenyl-ethanone) (UVATONE 8301, Upjohn).

It is known to those of ordinary skill in the art that the dehydrationby conventional means of the tertiary alcohols that are alpha to thecarbonyl groups is difficult. One conventional reaction that can be usedto dehydrate the phthaloylglycine-DAROCUR 2959 is by reacting thephthaloylglycine-DAROCUR 2959 in anhydrous benzene in the presence ofp-toluenesulfonic acid. After refluxing the mixture, the final productis isolated. However, the yield of the desired dehydrated alcohol isonly about 15 to 20% by this method.

To increase the yield of the desired dehydrated phthaloylglycine-DAROCUR2959, a new reaction was invented. The reaction is summarized asfollows: ##STR9##

It is to be understood that the groups on the carbon alpha to thecarbonyl group can be groups other than methyl groups such as aryl orheterocyclic groups. The only limitation on these groups are stericlimitations. Desirably, the metal salt used in the Nohr-MacDonaldelimination reaction is ZnCl₂. It is to be understood that othertransition metal salts can be used in performing the Nohr-MacDonaldelimination reaction but ZnCl₂ is the preferred metal salt. The amountof metal salt used in the Nohr-MacDonald elimination reaction ispreferably approximately equimolar to the tertiary alcohol compound,such as the photoreactor. The concentration of tertiary alcohol in thereaction solution is between approximately 4% and 50% w/v.

Thus, the stabilizing composition produced by the process of dehydratinga tertiary alcohol that is alpha to a carbonyl group on a photoreactoris shown in the following general formula: ##STR10## wherein R₁ ishydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or aheteroaryl group;

R₂ is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or aheteroaryl group;

R₃ is hydrogen, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or aheteroaryl group; and

R₄ is an aryl, heteroaryl, or substituted aryl group.

Another requirement of the reaction is that it be run in a non-aqueous,non-polar solvent. The preferred solvents for running the Nohr-MacDonaldelimination reaction are aromatic hydrocarbons including, but notlimited to, xylene, benzene, toluene, cumene, mesitylene, p-cymene,butylbenzene, styrene, and divinylbenzene. It is to be understood thatother substituted aromatic hydrocarbons can be used as solvents in thepresent invention. p-Xylene is the preferred aromatic hydrocarbonsolvent, but other isomers of xylene can be used in performing theNohr-MacDonald elimination reaction.

An important requirement in performing the Nohr-MacDonald eliminationreaction is that the reaction be run at a relatively high temperature.The reaction is desirably performed at a temperature of betweenapproximately 80° C. and 150° C. A suitable temperature for dehydratingphthaloylglycine-DAROCUR 2959 is approximately 124° C. The time thereaction runs is not critical. The reaction should be run betweenapproximately 30 minutes to 4 hours. However, depending upon thereactants and the solvent used, the timing may vary to achieve thedesired yield of product.

It is to be understood that the dehydrated phthaloylglycine-DAROCUR 2959can be attached to the molecular includant in a variety of ways. In oneembodiment, the dehydrated phthaloylglycine-DAROCUR 2959 is covalentlyattached to the cyclodextrin as shown in the following structure:##STR11##

In another embodiment, as shown below, only the modified DAROCUR 2959without the phthaloyl glycine attached is reacted with the cyclodextrinto yield the following compound. This compound is capable of stabilizinga dye that is associated with the molecular includant. It is to beunderstood that photoreactors other than DAROCUR 2959 can be used in thepresent invention. ##STR12##

In yet another embodiment, the dehydrated phthaloylglycine-DAROCUR 2959can be attached to the molecular includant via the opposite end of themolecule. One example of this embodiment is shown in the followingformula: ##STR13##

Another stabilizer that is considered part of the present invention isan arylketoalkene having the following general formula: ##STR14##wherein if R₁ is an aryl group, then R₂ is a hydrogen; heterocyclic;alkyl; aryl, or a phenyl group, the phenyl group optionally beingsubstituted with an alkyl, halo, amino, or a thiol group; and if R₂ isan aryl group, then R₁ is hydrogen; heterocyclic; alkyl; aryl, or aphenyl group, the phenyl group optionally being substituted with analkyl, halo, amino, or a thiol group. Preferably, the alkene group is inthe trans configuration.

Desirably, the arylketoalkene stabilizing compound has the followingformula. ##STR15##

The arylketoalkene may also function as a wavelength-specific sensitizerin the present invention, and it may be associated with any of thepreviously discussed photoreactors. One method of associating aphotoreactor with the arylketoalkene compound of the present inventionis described in Example 32. The arylketoalkene compound may optionallybe covalently bonded to the reactive species-generating photoinitiator.It is to be understood that the arylketoalkene compound of the presentinvention is not to be used with photoreactors in a composition wherestability in natural sunlight is desired. More particularly, as thearylketoalkene compounds absorb radiation in the range of about 270 to310 depending on the identity of R₁ and R₂, then these compounds arecapable of absorbing the appropriate radiation from sunlight.Accordingly, these compounds when admixed with a photoreactor can effecta mutation of the colorant upon exposure to sunlight. Where such achange in color is not desired, then a photoreactor is not to be admixedwith the arylketoalkene compound of the present invention, and thearylketoalkene compound is to be used with a colorant without aphotoreactor.

In the embodiment where the arylketoalkene compound is covalentlyattached to another molecule, whichever R₁ or R₂ that is an aryl groupwill have a group including, but not limited to, a carboxylic acidgroup, an aldehyde group, an amino group, a haloalkyl group, a hydroxylgroup, or a thioalkyl group attached thereto to allow the arylketoalkeneto be covalently bonded to the other molecule. Accordingly, thearylketoalkene stabilizing compound is represented by the followingformula: ##STR16##

Although it is preferred that the group attached to the aryl group ispara to the remainder of the stabilizer molecule, the group may also beortho or meta to the remainder of the molecule.

Accordingly, this embodiment of the present invention provides astabilizing arylketoalkene which, when associated with a colorant,stabilizes the colorant. Therefore, the above arylketoalkene can be usedas an additive to any colorant composition. For example, as thearylketoalkene compound is not water soluble, it can be directly addedto solvent or oil colorant compositions. Additionally, thearylketoalkene compound can be added to other colorant compositions thatcontain additives enabling the solubilization of the compound therein.

Further, the arylketoalkene stabilizing compounds can be solubilized inaqueous solution by a variety of means. One means of solubilizing thearylketoalkene stabilizing compound of the present invention is toattach the compound to a large water soluble molecule, such as acyclodextrin, as described in Examples 28 through 31. Desirably, betweenabout 1 and 12 arylketoalkene molecules can be attached to acyclodextrin molecule. More desirably, between about 4 to about 9arylketoalkene molecules are attached to a cyclodextrin molecule.Accordingly, the arylketoalkene compound attached to cyclodextrin can beadded to any aqueous colorant system to stabilize the colorant therein.It is to be understood that the stabilizing arylketoalkenes do not haveto be attached to the molecular includants to exhibit their stabilizingactivity.

Therefore, this embodiment provides a method for stabilizing colorantcompositions by admixing the aryketoalkene compound with the colorantcomposition in an amount effective to stabilize the composition. Thearylketoalkenes desirably should be present in the colorant medium orsolution at a concentration of approximately 0.1 to 50% by weight,desirably between approximately 20% and 30% by weight. If nocyclodextrin is used, the desirable range is approximately 1 part dye toapproximately 20 parts arylketoalkene.

Although the arylketoalkene compound need only be associated with thecolorant, in some embodiments of the present invention, thearylketoalkene compound may be covalently bonded to the colorant.

Although not wanting to be limited by the following, it is theorizedthat the arylketoalkene compound of the present invention stabilizescolorants through functioning as a singlet oxygen scavenger. In thealternative, it is theorized that the arylketoalkene compound functionsas a stabilizer of a colorant via the resonance of the unshared electronpairs in the p orbitals, e.g., it functions as an energy sink.

As a practical matter, the colorant, ultraviolet radiation transorber,modified photoreactor, arylketoalkene stabilizer, and molecularincludant are likely to be solids depending upon the constituents usedto prepare the molecules. However, any or all of such materials can be aliquid. The colored composition can be a liquid either because one ormore of its components is a liquid, or, when the molecular includant isorganic in nature, a solvent is employed. Suitable solvents include, butare not limited to, amides, such as N,N-dimethylformamide; sulfoxides,such as dimethylsulfoxide; ketones, such as acetone, methyl ethylketone, and methyl butyl ketone; aliphatic and aromatic hydrocarbons,such as hexane, octane, benzene, toluene, and the xylenes; esters, suchas ethyl acetate; water; and the like. When the molecular includant is acyclodextrin, particularly suitable solvents are the amides andsulfoxides.

In an embodiment where the composition of the present invention is asolid, the effectiveness of the above compounds on the colorant isimproved when the colorant and the selected compounds are in intimatecontact. To this end, the thorough blending of the components, alongwith other components which may be present, is desirable. Such blendinggenerally is accomplished by any of the means known to those havingordinary skill in the art. When the colored composition includes apolymer, blending is facilitated if the colorant and the ultravioletradiation transorber are at least partly soluble in softened or moltenpolymer. In such case, the composition is readily prepared in, forexample, a two-roll mill. Alternatively, the composition of the presentinvention can be a liquid because one or more of its components is aliquid.

For some applications, the composition of the present inventiontypically will be utilized in particulate form. In other applications,the particles of the composition should be very small. Methods offorming such particles are well known to those having ordinary skill inthe art.

The colored composition of the present invention can be utilized on orin any substrate. If one desires to mutate the colored composition thatis present in a substrate, however, the substrate should besubstantially transparent to the ultraviolet radiation which is employedto mutate the colorant. That is, the ultraviolet radiation will notsignificantly interact with or be absorbed by the substrate. As apractical matter, the composition typically will be placed on asubstrate, with the most common substrate being paper. Other substrates,including, but not limited to, woven and nonwoven webs or fabrics,films, and the like, can be used, however.

The colored composition optionally may also contain a carrier, thenature of which is well known to those having ordinary skill in the art.For many applications, the carrier will be a polymer, typically athermosetting or thermoplastic polymer, with the latter being the morecommon.

Further examples of thermoplastic polymers include, but are not limitedto: end-capped polyacetals, such as poly(oxymethylene) orpolyformaldehyde, poly(trichloroacetaldehyde), poly(n-valeraldehyde),poly(acetaldehyde), poly(propionaldehyde), and the like; acrylicpolymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylicacid), poly(ethyl acrylate), poly(methyl methacrylate), and the like;fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinatedethylenepropylene copolymers, ethylenetetrafluoroethylene copolymers,poly-(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylenecopolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and thelike; epoxy resins, such as the condensation products of epichlorohydrinand bisphenol A; polyamides, such as poly(6-aminocaproic acid) orpoly(ε-caprolactam), poly(hexamethylene adipamide), poly(hexamethylenesebacamide), poly(11-aminoundecanoic acid), and the like; polyaramides,such as poly(imino-1,3-phenyleneiminoisophthaloyl) or poly(m-phenyleneisophthalamide), and the like; parylenes, such as poly-p-xylylene,poly(chloro-p-xylene), and the like; polyaryl ethers, such aspoly(oxy-2,6-dimethyl-1,4-phenylene) or poly(p-phenylene oxide), and thelike; polyaryl sulfones, such aspoly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene-isopropylidene-1,4-phenylene),poly(sulfonyl-1,4-phenyleneoxy-1,4-phenylenesulfonyl-4,4-biphenylene),and the like; polycarbonates, such as poly(bisphenol A) orpoly(carbonyldioxy-1,4-phenyleneisopropylidene-1,4-phenylene), and thelike; polyesters, such as poly(ethylene terephthalate),poly(tetramethylene terephthalate), poly(cyclohexylene-1,4-dimethyleneterephthalate) orpoly(oxymethylene-1,4-cyclohexylenemethyleneoxyterephthaloyl), and thelike; polyaryl sulfides, such as poly(p-phenylene sulfide) orpoly(thio-1,4-phenylene), and the like; polyimides, such aspoly(pyromellitimido-1,4-phenylene), and the like; polyolefins, such aspolyethylene, polypropylene, poly(1-butene), poly(2-butene),poly(1-pentene), poly(2-pentene), poly(3-methyl-1-pentene),poly(4-methyl-1-pentene), 1,2-poly-1,3-butadiene,1,4-poly-1,3-butadiene, polyisoprene, polychloroprene,polyacrylonitrile, poly(vinyl acetate), poly(vinylidene chloride),polystyrene, and the like; and copolymers of the foregoing, such asacrylonitrilebutadienestyrene (ABS) copolymers,styrene-n-butylmethacrylate copolymers, ethylene-vinyl acetatecopolymers, and the like.

Some of the more commonly used thermoplastic polymers includestyrene-n-butyl methacrylate copolymers, polystyrene, styrene-n-butylacrylate copolymers, styrene-butadiene copolymers, polycarbonates,poly(methyl methacrylate), poly(vinylidene fluoride), polyamides(nylon-12), polyethylene, polypropylene, ethylene-vinyl acetatecopolymers, and epoxy resins.

Examples of thermosetting polymers include, but are not limited to,alkyd resins, such as phthalic anhydride-glycerol resins, maleicacid-glycerol resins, adipic acid-glycerol resins, and phthalicanhydride-pentaerythritol resins; allylic resins, in which such monomersas diallyl phthalate, diallyl isophthalate diallyl maleate, and diallylchlorendate serve as nonvolatile cross-linking agents in polyestercompounds; amino resins, such as aniline-formaldehyde resins, ethyleneurea-formaldehyde resins, dicyandiamide-formaldehyde resins,melamine-formaldehyde resins, sulfonamide-formaldehyde resins, andurea-formaldehyde resins; epoxy resins, such as cross-linkedepichlorohydrinbisphenol A resins; phenolic resins, such asphenol-formaldehyde resins, including Novolacs and resols; andthermosetting polyesters, silicones, and urethanes.

In addition to the colorant, and ultraviolet radiation transorber orfunctionalized molecular includant, modified photoreactor,arylketoalkene stabilizer, and optional carrier, the colored compositionof the present invention also can contain additional components,depending upon the application for which it is intended. Examples ofsuch additional components include, but are not limited to, chargecarriers, stabilizers against thermal oxidation, viscoelastic propertiesmodifiers, cross-linking agents, plasticizers, charge control additivessuch as a quaternary ammonium salt; flow control additives such ashydrophobic silica, zinc stearate, calcium stearate, lithium stearate,polyvinylstearate, and polyethylene powders; and fillers such as calciumcarbonate, clay and talc, among other additives used by those havingordinary skill in the art. Charge carriers are well known to thosehaving ordinary skill in the art and typically are polymer-coated metalparticles. The identities and amounts of such additional components inthe colored composition are well known to one of ordinary skill in theart.

The present invention is further described by the examples which follow.Such examples, however, are not to be construed as limiting in any wayeither the spirit or scope of the present invention. In the examples,all parts are parts by weight unless stated otherwise.

EXAMPLE 1

This example describes the preparation of a β-cyclodextrin molecularincludant having (1) an ultraviolet radiation transorber covalentlybonded to the cyclodextrin outside of the cavity of the cyclodextrin,and (2) a colorant associated with the cyclodextrin by means of hydrogenbonds and/or van der Waals forces.

A. Friedel-Crafts Acylation of Transorber

A 250-ml, three-necked, round-bottomed reaction flask was fitted with acondenser and a pressure-equalizing addition funnel equipped with anitrogen inlet tube. A magnetic stirring bar was placed in the flask.While being flushed with nitrogen, the flask was charged with 10 g (0.05mole) of 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184, Ciba-GeigyCorporation, Hawthorne, N.Y.), 100 ml of anhydrous tetrahydofuran(Aldrich Chemical Company, Inc., Milwaukee, Wis.), and 5 g (0.05 mole)of succinic anhydride (Aldrich Chemical Co., Milwaukee, Wis.). To thecontinuously stirred contents of the flask then was added 6.7 g ofanhydrous aluminum chloride (Aldrich Chemical Co., Milwaukee, Wis.). Theresulting reaction mixture was maintained at about 0° C. in an ice bathfor about one hour, after which the mixture was allowed to warm toambient temperature for two hours. The reaction mixture then was pouredinto a mixture of 500 ml of ice water and 100 ml of diethyl ether. Theether layer was removed after the addition of a small amount of sodiumchloride to the aqueous phase to aid phase separation. The ether layerwas dried over anhydrous magnesium sulfate. The ether was removed underreduced pressure, leaving 12.7 g (87 percent) of a white crystallinepowder. The material was shown to be 1-hydroxycyclohexyl4-(2-carboxyethyl)carbonylphenyl ketone by nuclear magnetic resonanceanalysis.

B. Preparation of Acylated Transorber Acid Chloride

A 250-ml round-bottomed flask fitted with a condenser was charged with12.0 g of 1-hydroxycyclohexyl 4-(2-carboxyethyl)carbonylphenyl ketone(0.04 mole), 5.95 g (0.05 mole) of thionyl chloride (Aldrich ChemicalCo., Milwaukee, Wis.), and 50 ml of diethyl ether. The resultingreaction mixture was stirred at 30° C. for 30 minutes, after which timethe solvent was removed under reduced pressure. The residue, a whitesolid, was maintained at 0.01 Torr for 30 minutes to remove residualsolvent and excess thionyl chloride, leaving 12.1 g (94 percent) of1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone.

C. Covalent Bonding of Acylated Transorber to Cyclodextrin

A 250-ml, three-necked, round-bottomed reaction flask containing amagnetic stirring bar and fitted with a thermometer, condenser, andpressure-equalizing addition funnel equipped with a nitrogen inlet tubewas charged with 10 g (9.8 mmole) of β-cyclodextrin (AmericanMaize-Products Company, Hammond, Ind.), 31.6 g (98 mmoles) of1-hydroxycyclohexyl 4-(2-chloroformylethyl)carbonylphenyl ketone, and100 ml of N,N-dimethylformamide while being continuously flushed withnitrogen. The reaction mixture was heated to 50° C. and 0.5 ml oftriethylamine added. The reaction mixture was maintained at 50° C. foran hour and allowed to cool to ambient temperature. In this preparation,no attempt was made to isolate the product, a β-cyclodextrin to which anultraviolet radiation transorber had been covalently coupled (referredto hereinafter for convenience as β-cyclodextrin-transorber).

The foregoing procedure was repeated to isolate the product of thereaction. At the conclusion of the procedure as described, the reactionmixture was concentrated in a rotary evaporator to roughly 10 percent ofthe original volume. The residue was poured into ice water to whichsodium chloride then was added to force the product out of solution. Theresulting precipitate was isolated by filtration and washed with diethylether. The solid was dried under reduced pressure to give 24.8 g of awhite powder. In a third preparation, the residue remaining in therotary evaporator was placed on top of an approximately 7.5-cm columncontaining about 15 g of silica gel. The residue was eluted withN,N-dimethylformamide, with the eluant being monitored by means ofWhatman® Flexible-Backed TLC Plates (Catalog No. 05-713-161, FisherScientific, Pittsburgh, Pa.). The eluted product was isolated byevaporating the solvent. The structure of the product was verified bynuclear magnetic resonance analysis.

D. Association of Colorant with Cyclodextrin-Transorber-Preparation ofColored Composition

To a solution of 10 g (estimated to be about 3.6 mmole) ofβ-cyclodextrin-transorber in 150 ml of N,N-dimethylformamide in a 250-mlround-bottomed flask was added at ambient temperature 1.2 g (3.6 mmole)of Malachite Green oxalate (Aldrich Chemical Company, Inc., Milwaukee,Wis.), referred to hereinafter as Colorant A for convenience. Thereaction mixture was stirred with a magnetic stirring bar for one hourat ambient temperature. Most of the solvent then was removed in a rotaryevaporator and the residue was eluted from a silica gel column asalready described. The β-cyclodextrin-transorber Colorant A inclusioncomplex moved down the column first, cleanly separating from both freeColorant A and β-cyclodextrin-transorber. The eluant containing thecomplex was collected and the solvent removed in a rotary evaporator.The residue was subjected to a reduced pressure of 0.01 Torr to removeresidual solvent to yield a blue-green powder.

E. Mutation of Colored Composition

The β-cyclodextrin-transorber Colorant A inclusion complex was exposedto ultraviolet radiation from two different lamps, Lamps A and B. Lamp Awas a 222-nanometer excimer lamp assembly organized in banks of fourcylindrical lamps having a length of about 30 cm. The lamps were cooledby circulating water through a centrally located or inner tube of thelamp and, as a consequence, they operated at a relatively lowtemperature, i.e., about 50° C. The power density at the lamp's outersurface typically is in the range of from about 4 to about 20 joules persquare meter (J/m²). However, such range in reality merely reflects thecapabilities of current excimer lamp power supplies; in the future,higher power densities may be practical. The distance from the lamp tothe sample being irradiated was 4.5 cm. Lamp B was a 500-watt Hanoviamedium pressure mercury lamp (Hanovia Lamp Co., Newark, N.J.). Thedistance from Lamp B to the sample being irradiated was about 15 cm.

A few drops of an N,N-dimethylformamide solution of theβ-cyclodextrin-transorber Colorant A inclusion complex were placed on aTLC plate and in a small polyethylene weighing pan. Both samples wereexposed to Lamp A and were decolorized (mutated to a colorless state) in15-20 seconds. Similar results were obtained with Lamp B in 30 seconds.

A first control sample consisting of a solution of Colorant A andβ-cyclodextrin in N,N-dimethylformamide was not decolorized by Lamp A. Asecond control sample consisting of Colorant A and 1-hydroxycyclohexylphenyl ketone in N,N-dimethylformamide was decolorized by Lamp A within60 seconds. On standing, however, the color began to reappear within anhour.

To evaluate the effect of solvent on decolorization, 50 mg of theβ-cyclodextrin-transorber Colorant A inclusion complex was dissolved in1 ml of solvent. The resulting solution or mixture was placed on a glassmicroscope slide and exposed to Lamp A for 1 minute. The rate ofdecolorization, i.e., the time to render the sample colorless, wasdirectly proportional to the solubility of the complex in the solvent,as summarized below.

                  TABLE 1                                                         ______________________________________                                                                    Decolorization                                    Solvent          Solubility Time                                              ______________________________________                                        N,N-Dimethylformamide                                                                          Poor        1 minute                                         Dimethylsulfoxide                                                                              Soluble    <10 seconds                                       Acetone          Soluble    <10 seconds                                       Hexane           Insoluble    --                                              Ethyl Acetate    Poor        1 minute                                         ______________________________________                                    

Finally, 10 mg of the β-cyclodextrin-transorber Colorant A inclusioncomplex were placed on a glass microscope slide and crushed with apestle. The resulting powder was exposed to Lamp A for 10 seconds. Thepowder turned colorless. Similar results were obtained with Lamp B, butat a slower rate.

EXAMPLE 2

Because of the possibility in the preparation of the colored compositiondescribed in the following examples for the acylated transorber acidchloride to at least partially occupy the cavity of the cyclodextrin, tothe partial or complete exclusion of colorant, a modified preparativeprocedure was carried out. Thus, this example describes the preparationof a β-cyclodextrin molecular includant having (1) a colorant at leastpartially included within the cavity of the cyclodextrin and associatedtherewith by means of hydrogen bonds and/or van der Waals forces, and(2) an ultraviolet radiation transorber covalently bonded to thecyclodextrin substantially outside of the cavity of the cyclodextrin.

A. Association of Colorant with a Cyclodextrin

To a solution of 10.0 g (9.8 mmole) of β-cyclodextrin in 150 ml ofN,N-dimethylformamide was added 3.24 g (9.6 mmoles) of Colorant A. Theresulting solution was stirred at ambient temperature for one hour. Thereaction solution was concentrated under reduced pressure in a rotaryevaporator to a volume about one-tenth of the original volume. Theresidue was passed over a silica gel column as described in Part C ofExample 1. The solvent in the eluant was removed under reduced pressurein a rotary evaporator to give 12.4 g of a blue-green powder,β-cyclodextrin Colorant A inclusion complex.

B. Covalent Bonding of Acylated Transorber to Cyclodextrin ColorantInclusion Complex-Preparation of Colored Composition

A 250-ml, three-necked, round-bottomed reaction flask containing amagnetic stirring bar and fitted with a thermometer, condenser, andpressure-equalizing addition funnel equipped with a nitrogen inlet tubewas charged with 10 g (9.6 mmole) of β-cyclodextrin Colorant A inclusioncomplex, 31.6 g (98 mmoles) of 1-hydroxycyclohexyl4-(2-chloroformylethyl)carbonylphenyl ketone prepared as described inPart B of Example 1, and 150 ml of N,N-dimethylformamide while beingcontinuously flushed with nitrogen. The reaction mixture was heated to50° C. and 0.5 ml of triethylamine added. The reaction mixture wasmaintained at 50° C. for an hour and allowed to cool to ambienttemperature. The reaction mixture then was worked up as described inPart A, above, to give 14.2 g of β-cyclodextrin-transorber Colorant Ainclusion complex, a blue-green powder.

C. Mutation of Colored Composition

The procedures described in Part E of Example 1 were repeated with theβ-cyclodextrin-transorber Colorant A inclusion complex prepared in PartB, above, with essentially the same results.

EXAMPLE 3

This example describes a method of preparing an ultraviolet radiationtransorber, 2- p-(2-methyllactoyl)phenoxy!ethyl1,3-dioxo-2-isoindolineacetate, designated phthaloylglycine-DAROCUR2959.

The following was admixed in a 250 ml, three-necked, round bottomedflask fitted with a Dean & Stark adapter with condenser and two glassstoppers: 20.5 g (0.1 mole) of the wavelength selective sensitizer,phthaloylglycine (Aldrich Chemical Co., Milwaukee, Wis.); 24.6 g (0.1mole) of the photoreactor, DAROCUR 2959 (Ciba-Geigy, Hawthorne, N.Y.);100 ml of benzene (Aldrich Chemical Co., Milwaukee, Wis.); and 0.4 gp-toluenesulfonic acid (Aldrich Chemical Co., Milwaukee, Wis.). Themixture was heated at reflux for 3 hours after which time 1.8 ml ofwater was collected. The solvent was removed under reduced pressure togive 43.1 g of white powder. The powder was recrystallized from 30%ethyl acetate in hexane (Fisher) to yield 40.2 g (93%) of a whitecrystalline powder having a melting point of 153°-4° C. The reaction issummarized as follows: ##STR17##

The resulting product, designated phthaloylglycine-DAROCUR 2959, had thefollowing physical parameters:

IR NUJOL MULL! v_(max) 3440, 1760, 1740, 1680, 1600 cm-1

1H NMR CDC13! ∂ppm 1.64 s!, 4.25 m!, 4.49 m!, 6.92 m!, 7.25 m!, 7.86 m!,7.98 m!, 8.06 m! ppm

EXAMPLE 4

This example describes a method of dehydrating thephthaloylglycine-DAROCUR 2959 produced in Example 3.

The following was admixed in a 250 ml round bottomed flask fitted with aDean & Stark adapter with condenser: 21.6 g (0.05 mole)phthaloylglycine-DAROCUR 2959; 100 ml of anhydrous benzene (AldrichChemical Co., Milwaukee, Wis.); and 0.1 g p-toluenesulfonic acid(Aldrich Chemical Co., Milwaukee, Wis.). The mixture was refluxed for 3hours. After 0.7 ml of water had been collected in the trap, thesolution was then removed under vacuum to yield 20.1 g (97%) of a whitesolid. However, analysis of the white solid showed that this reactionyielded only 15 to 20% of the desired deydration product. The reactionis summarized as follows: ##STR18##

The resulting reaction product had the following physical parameters:

IR (NUJOL) v_(max) 1617cm-1 (C═C-C═O)

EXAMPLE 5

This example describes the Nohr-MacDonald elimination reaction used todehydrate the phthaloylglycine-DAROCUR 2959 produced in Example 3.

Into a 500 ml round bottomed flask were placed a stirring magnet, 20.0 g(0.048 mole) of the phthaloylglycine-DAROCUR 2959, and 6.6 g (0.048mole) of anhydrous zinc chloride (Aldrich Chemical Co., Milwaukee,Wis.). 250 ml of anhydrous p-xylene (Aldrich Chemical Co., Milwaukee,Wis.) was added and the mixture refluxed under argon atmosphere for twohours. The reaction mixture was then cooled, resulting in a whiteprecipitate which was collected. The white powder was thenrecrystallized from 20% ethyl acetate in hexane to yield 18.1 g (95%) ofa white powder. The reaction is summarized as follows: ##STR19##

The resulting reaction product had the following physical parameters:

Melting Point: 138° C. to 140° C.; Mass spectrum: m/e: 393 M +, 352,326, 232, 160; IR (KB) v_(max) 1758, 1708, 1677, 1600 cm-1 1HNMR DMSO!∂ppm 1.8(s), 2.6(s), 2.8 (d), 3.8 (d), 4.6 (m), 4.8 (m), 7.3(m), 7.4(m), 8.3 (m), and 8.6 (d); 13C NMR DMSO! ∂ppm 65.9 (CH2═)

EXAMPLE 6

This example describes a method of producing a β-cyclodextrin havingdehydrated phthaloylglycine-DAROCUR 2959 groups from Example 4 or 5covalently bonded thereto.

The following was admixed in a 100 ml round-bottomed flask: 5.0 g (4mmole) β-cyclodextrin (American Maize Product Company, Hammond, Ind.)(designated β-CD in the following reaction); 8.3 g (20 mmole) dehydratedphthaloylglycine-DAROCUR 2959; 50 ml of anhydrous DMF; 20 ml of benzene;and 0.01 g p-tolulenesulfonyl chloride (Aldrich Chemical Co., Milwaukee,Wis.). The mixture was chilled in a salt/ice bath and stirred for 24hours. The reaction mixture was poured into 150 ml of weak sodiumbicarbonate solution and extracted three times with 50 ml ethyl ether.The aqueous layer was then filtered to yield a white solid comprisingthe β-cyclodextrin with phthaloylglycine-DAROCUR 2959 group attached. Ayield of 9.4 g was obtained. Reverse phase TLC plate using a 50:50DMF:acetonitrile mixture showed a new product peak compared to thestarting materials. ##STR20##

The β-cyclodextrin molecule has several primary alcohols and secondaryalcohols with which the phthaloylglycine-DAROCUR 2959 can react. Theabove representative reaction only shows a single phthaloylglycine-2959molecule for illustrative purposes.

EXAMPLE 7

This example describes a method of associating a colorant and anultraviolet radiation transorber with a molecular includant. Moreparticularly, this example describes a method of associating thecolorant crystal violet with the molecular includant β-cyclodextrincovalently bonded to the ultraviolet radiation transorber dehydratedphthaloylglycine-DAROCUR 2959 of Example 6.

The following was placed in a 100 ml beaker: 4.0 g β-cyclodextrin havinga dehydrated phthaloylglycine-DAROCUR 2959 group; and 50 ml of water.The water was heated to 70° C. at which point the solution became clear.Next, 0.9 g (2.4 mmole) crystal violet (Aldrich Chemical Company,Milwaukee, Wis.) was added to the solution, and the solution was stirredfor 20 minutes. Next, the solution was then filtered. The filtrand waswashed with the filtrate and then dried in a vacuum oven at 84° C. Aviolet-blue powder was obtained having 4.1 g (92%) yield. The resultingreaction product had the following physical parameters:

U.V. Spectrum DMF v_(max) 610 nm (cf cv v_(max) 604 nm)

EXAMPLE 8

This example describes a method of producing the ultraviolet radiationtransorber 4(4-hydroxyphenyl) butan-2-one-DAROCUR 2995 (chlorosubstituted).

The following was admixed in a 250 ml round-bottomed flask fitted with acondenser and magnetic stir bar: 17.6 g (0.1 mole) of the wavelengthselective sensitizer, 4(4-hydroxyphenyl) butan-2-one (Aldrich ChemicalCompany, Milwaukee, Wis.); 26.4 g (0.1 mole) of the photoreactor, chlorosubstituted DAROCUR 2959 (Ciba-Geigy Corporation, Hawthorne, N.Y.); 1.0ml of pyridine (Aldrich Chemical Company, Milwaukee, Wis.); and 100 mlof anhydrous tetrahydrofuran (Aldrich Chemical Company, Milwaukee,Wis.). The mixture was refluxed for 3 hours and the solvent partiallyremoved under reduced pressure (60% taken off). The reaction mixture wasthen poured into ice water and extracted with two 50 ml aliquots ofdiethyl ether. After drying over anhydrous magnesium sulfate and removalof solvent, 39.1 g of white solvent remained. Recrystallization of thepowder from 30% ethyl acetate in hexane gave 36.7 g (91%) of a whitecrystalline powder, having a melting point of 142°-3° C. The reaction issummarized in the following reaction: ##STR21##

The resulting reaction product had the following physical parameters:

IR NUJOL MULL! v_(max) 3460, 1760, 1700, 1620, 1600 cm-1

1H CDC13! ∂ppm 1.62 s!, 4.2 m!, 4.5 m!, 6.9 m! ppm

The ultraviolet radiation transorber produced in this example,4(4-hydroxyphenyl) butan-2-one-DAROCUR 2959 (chloro substituted), may beassociated with β-cyclodextrin and a colorant such as crystal violet,using the methods described above wherein 4(4-hydroxyphenyl)butan-2-one-DAROCUR 2959 (chloro substituted) would be substituted forthe dehydrated phthaloylglycine-DAROCUR 2959.

EXAMPLE 9 Stabilizing activity of the radiation transorber

This example demonstrates the ability of the present invention tostabilize colorants against light. Victoria Pure Blue BO is admixed inacetonitrile with phthaloylglycine-DAROCUR 2959, represented by thefollowing formula: ##STR22## and dehydrated phthaloylglycine-DAROCUR2959, represented by the following formula: ##STR23##

Solutions were prepared according to Table 2. The dye solutions werecarefully, uniformly spread on steel plates to a thickness ofapproximately 0.1 mm. The plates were then immediately exposed to amedium pressure 1200 watt high intensity quartz arc mercury dischargelamp (Conrad-Hanovia, Inc., Newark, N.J.) at a distance of 30 cm fromthe light. The mercury discharge light is a source of high intensity,broad spectrum light that is used in accelerated fading analyses. Table2 shows the results of the fade time with the various solutions. Fadetime is defined as the time until the dye became colorless to the nakedeye.

                  TABLE 2                                                         ______________________________________                                                       Victoria pure                                                                           Fade                                                                Blue BO   Time                                                 ______________________________________                                        Phthaloylglycine-Darocur 2959                                                  3 parts by weight                                                                             1 part by weight                                                                          2       min                                      10 parts by weight                                                                             1 part by weight                                                                          11/2    min                                      20 parts by weight                                                                             1 part by weight                                                                          30      sec                                      Dehydrated                                                                    Phthaloylglycine-Darocur 2959                                                  3 parts by weight                                                                             1 part by weight                                                                          4       min                                      10 parts by weight                                                                             1 part by weight                                                                          8       min                                      20 parts by weight                                                                             1 part by weight                                                                          >10     min                                      ______________________________________                                    

As can be seen in Table 2, when phthaloylglycine-DAROCUR 2959 wasadmixed with Victoria Pure Blue BO, the dye faded when exposed to themercury discharge light. However, when dehydratedphthaloylglycine-DAROCUR 2959 was admixed with the Victoria Pure Blue BOat a ratio of 10 parts dehydrated phthaloylglycine-2959 to one partVictoria Pure Blue BO, there was increased stabilization of the dye tolight. When the ratio was 20 parts dehydrated phthaloylglycine-DAROCUR2959 to one part Victoria Pure Blue BO, the dye was substantiallystabilized to the mercury discharge light in the time limits of theexposure.

EXAMPLE 10

To determine whether the hydroxy and the dehydroxy DAROCUR 2959 have thecapability to stabilize colorants the following experiment wasconducted. The following two compounds were tested as described below:##STR24## 20 parts by weight of the hydroxy and the dehydroxy DAROCUR2959 were admixed separately to one part by weight of Victoria Pure BlueBO in acetonitrile. The dye solutions were uniformly spread on steelplates to a thickness of approximately 0.1 mm. The plates were thenimmediately exposed to a mercury discharge light at a distance of 30 cmfrom the light. The mercury discharge light is a source of highintensity, broad spectrum light that is used in accelerated fadinganalyses. Table 3 shows the results of the fade time with the varioussolutions. Fade time is defined as the time until the dye becamecolorless to the naked eye.

                  TABLE 3                                                         ______________________________________                                                          Victoria Pure                                               Compound          Blue      Fade Time                                         ______________________________________                                        20 parts 2959 (Hydroxy)                                                                         1 part    <2 min                                            20 parts 2959 (Dehydroxy)                                                                       1 part    <2 min                                            None              1 part    <2 min                                            ______________________________________                                    

EXAMPLE 11

Stabilizing activity of the radiation transorber and a molecularincludant

This example demonstrates the capability of dehydratedphthaloylglycine-DAROCUR 2959 bound to β-cyclodextrin to stabilize dyesagainst light. The Victoria Pure Blue BO associated with the radiationtransorber, as discussed in the examples above, was tested to determineits capability to stabilize the associated dye against light emittedfrom a mercury discharge light. In addition, the Victoria Pure Blue BOalone and Victoria Pure Blue BO admixed with β-cyclodextrin were testedas controls. The compositions tested were as follows:

1. Victoria Pure Blue BO only at a concentration of 10 mg/ml inacetonitrile.

2. Victoria Pure Blue BO included in β-cyclodextrin at a concentrationof 20 mg/ml in acetonitrile.

3. The Victoria Pure Blue BO included in β-cyclodextrin to which theradiation transorber (dehydrated phthaloylglycine-DAROCUR 2959) iscovalently attached at a concentration of 20 mg/ml in acetonitrile.

The protocol for testing the stabilizing qualities of the threecompositions is as follows: the dye solutions were carefully, uniformlyspread on steel plates to a thickness of approximately 0.1 mm. Theplates were then immediately exposed to a medium pressure 1200 watt highintensity quartz arc mercury discharge lamp (Conrad-Hanovia, Inc.,Newark, N.J.) at a distance of 30 cm from the lamp.

                  TABLE 4                                                         ______________________________________                                        Composition          Fade Time                                                ______________________________________                                        1                     5 sec                                                   2                     5 sec                                                   3                    >10 minutes.sup.a                                        ______________________________________                                         .sup.a There is a phase change after 10 minutes due to extreme heat      

As shown in Table 4, only composition number 3, the Victoria Pure BlueBO included in cyclodextrin with the radiation transorber covalentlyattached to the β-cyclodextrin was capable of stabilizing the dye underthe mercury discharge light.

EXAMPLE 12

Preparation of epoxide intermediate of dehydratedphthaloylglycine-DAROCUR 2959

The epoxide intermediate of dehydrated phthaloylglycine-DAROCUR 2959 wasprepared according to the following reaction: ##STR25##

In a 250 ml, three-necked, round bottomed flask fitted with an additionfunnel, thermometer and magnetic stirrer was placed 30.0 g (0.076 mol)of the dehydrated phthaloylglycine-DAROCUR 2959, 70 ml methanol and 20.1ml hydrogen peroxide (30% solution). The reaction mixture was stirredand cooled in a water/ice bath to maintain a temperature in the range15°-20° C. 5.8 ml of a 6 N NaOH solution was placed in the additionfunnel and the solution was slowly added to maintain the reactionmixture temperature of 15°-20° C. This step took about 4 minutes. Themixture was then stirred for 3 hours at about 20°-25° C. The reactionmixture was then poured into 90 ml of water and extracted with two 70 mlportions of ethyl ether. The organic layers were combined and washedwith 100 ml of water, dried with anhydrous MgSO₄, filtered, and theether removed on a rotary evaporator to yield a white solid (yield 20.3g, 65%). The IR showed the stretching of the C--O--C group and thematerial was used without further purification.

EXAMPLE 13

Attachment of epoxide intermediate to thiol cyclodextrin

The attachment of the, epoxide intermediate of dehydratedphthaloylglycine-DAROCUR 2959 was done according to the followingreaction: ##STR26##

In a 250 ml 3-necked round bottomed flask fitted with a stopper and twoglass stoppers, all being wired with copper wire and attached to theflask with rubber bands, was placed 30.0 g (0.016 mol) thiolcyclodextrin and 100 ml of anhydrous dimethylformamide (DMF) (AldrichChemical Co., Milwaukee, Wis.). The reaction mixture was cooled in a icebath and 0.5 ml diisopropyl ethyl amine was added. Hydrogen sulfide wasbubbled into the flask and a positive pressure maintained for 3 hours.During the last hour, the reaction mixture was allowed to warm to roomtemperature.

The reaction mixture was flushed with argon for 15 minutes and thenpoured into 70 ml of water to which was then added 100 ml acetone. Awhite precipitate occurred and was filtered to yield 20.2 g (84.1%) of awhite powder which was used without further purification.

In a 250 ml round bottomed flask fitted with a magnetic stirrer andplaced in an ice bath was placed 12.7 (0.031 mol), 80 ml of anhydrousDMF (Aldrich Chemical Co., Milwaukee, Wis.) and 15.0 g (0.010 mol) thiolCD. After the reaction mixture was cooled, 0.5 ml of diisopropyl ethylamine was added and the reaction mixture stirred for 1 hour at 0° C. to5° C. followed by 2 hours at room temperature. The reaction mixture wasthen poured into 200 ml of ice water and a white precipitate formedimmediately. This was filtered and washed with acetone. The damp whitepowder was dried in a convection oven at 80° C. for 3 hours to yield awhite powder. The yield was 24.5 g (88%).

EXAMPLE 14

Insertion of Victoria Pure Blue in the cyclodextrin cavity

In a 250 ml Erlenmeyer flask was placed a magnetic stirrer, 40.0 g(0.014 mol) of the compound produced in Example 13 and 100 ml water. Theflask was heated on a hot plate to 80° C. When the white cloudy mixturebecame clear, 7.43 g (0.016 mol) of Victoria Pure Blue BO powder wasthen added to the hot solution and stirred for 10 minutes then allowedto cool to 50° C. The contents were then filtered and washed with 20 mlof cold water.

The precipitate was then dried in a convention oven at 80° C. for 2hours to yield a blue powder 27.9 g (58.1%).

EXAMPLE 15

The preparation of a tosylated cyclodextrin with the dehydroxyphthaloylglycine-DAROCUR 2959 attached thereto is performed by thefollowing reactions: ##STR27##

To a 500 ml 3-necked round bottomed flask fitted with a bubble tube,condenser and addition funnel, was placed 10 g (0.025 mole) of thedehydrated phthaloylglycine-DAROCUR 2959 in 150 ml of anhydrousN,N-diethylformamide (Aldrich Chemical Co., Milwaukee, Wis.) cooled to0° C. in an ice bath and stirred with a magnetic stirrer. The synthesiswas repeated except that the flask was allowed to warm up to 60° C.using a warm water bath and the H₂ S pumped into the reaction flask tillthe stoppers started to move (trying to release the pressure). The flaskwas then stirred under these conditions for 4 hours. The saturatedsolution was kept at a positive pressure of H₂ S. The stoppers were helddown by wiring and rubber bands. The reaction mixture was then allowedto warm-up overnight. The solution was then flushed with argon for 30minutes and the reaction mixture poured onto 50 g of crushed ice andextracted three times (3×80 ml) with diethyl ether (Aldrich ChemicalCo., Milwaukee, Wis.).

The organic layers were condensed and washed with water and dried withMgSO₄. Removal of the solvent on a rotary evaporator gave 5.2 g of acrude product. The product was purified on a silica column using 20%ethyl acetate in hexane as eluant. 4.5 g of a white solid was obtained.

A tosylated cyclodextrin was prepared according to the followingreaction: ##STR28##

To a 100 ml round bottomed flask was placed 6.0 g β-cyclodextrin(American Maize Product Company), 10.0 g (0.05 mole) p-toluenesulfonylchloride (Aldrich Chemical Co., Milwaukee, Wis.), 50 ml of pH 10 buffersolution (Fisher). The resultant mixture was stirred at room temperaturefor 8 hours after which it was poured on ice (approximately 100 g) andextracted with diethyl ether. The aqueous layer was then poured into 50ml of acetone (Fisher) and the resultant, cloudy mixture filtered. Theresultant white powder was then run through a sephadex column (AldrichChemical Co., Milwaukee, Wis.) using n-butanol, ethanol, and water(5:4:3 by volume) as eluant to yield a white powder. The yield was10.9%.

The degree of substitution of the white powder (tosyl-cyclodextrin) wasdetermined by ¹³ C NMR spectroscopy (DMF-d6) by comparing the ratio ofhydroxysubstituted carbons versus tosylated carbons, both at the 6position. When the 6-position carbon bears a hydroxy group, the NMRpeaks for each of the six carbon atoms are given in Table 5.

                  TABLE 5                                                         ______________________________________                                        Carbon Atom   NMR Peak (ppm)                                                  ______________________________________                                        1             101.8                                                           2             72.9                                                            3             72.3                                                            4             81.4                                                            5             71.9                                                            6             59.8                                                            ______________________________________                                    

The presence of the tosyl group shifts the NMR peaks of the 5-positionand 6-position carbon atoms to 68.8 and 69.5 ppm, respectively.

The degree of substitution was calculated by integrating the NMR peakfor the 6-position tosylated carbon, integrating the NMR peak for the6-position hydroxy-substituted carbon, and dividing the former by thelatter. The integrations yielded 23.6 and 4.1, respectively, and adegree of substitution of 5.9. Thus, the average degree of substitutionin this example is about 6.

The tosylated cyclodextrin with the dehydroxy phthaloylglycine-DAROCUR2959 attached was prepared according to the following reaction:##STR29##

To a 250 ml round bottomed flask was added 10.0 g (4-8 mole) oftosylated substituted cyclodextrin, 20.7 (48 mmol) of thiol (mercaptodehydrated phthaloylglycine-DAROCUR 2959) in 100 ml of DMF. The reactionmixture was cooled to 0° C. in an ice bath and stirred using a magneticstirrer. To the solution was slowly dropped in 10 ml of ethyldiisopropylamine (Aldrich Chemical Co., Milwaukee, Wis.) in 20 ml ofDMF. The reaction was kept at 0° C. for 8 hours with stirring. Thereaction mixture was extracted with diethyl ether. The aqueous layer wasthen treated with 500 ml of acetone and the precipitate filtered andwashed with acetone. The product was then run on a sephadex column usingn-butanol, ethanol, and water (5:4:3 by volume) to yield a white powder.The yield was 16.7 g.

The degree of substitution of the functionalized molecular includant wasdetermined as described above. In this case, the presence of thederivatized ultraviolet radiation transorber shifts the NMR peak of the6-position carbon atom to 63.1. The degree of substitution wascalculated by integrating the NMR peak for the 6-position substitutedcarbon, integrating the NMR peak for the 6-position hydroxy-substitutedcarbon, and dividing the former by the latter. The integrations yielded67.4 and 11.7, respectively, and a degree of substitution of 5.7. Thus,the average degree of substitution in this example is about 6. Thereaction above shows the degree of substitution to be "n". Although nrepresents the value of substitution on a single cyclodextrin, andtherefore, can be from 0 to 24, it is to be understood that the averagedegree of substitution is about 6.

EXAMPLE 16

The procedure of Example 15 was repeated, except that the amounts ofβ-cyclodextrin and p-toluenesulfonic acid (Aldrich) were 6.0 g and 5.0g, respectively. In this case, the degree of substitution of thecyclodextrin was found to be about 3.

EXAMPLE 17

The procedure of Example 15 was repeated, except that the derivatizedmolecular includant of Example 16 was employed in place of that fromExample 15. The average degree of substitution of the functionalizedmolecular includant was found to be about 3.

EXAMPLE 18

This example describes the preparation of a colored composition whichincludes a mutable colorant and the functionalized molecular includantfrom Example 15.

In a 250-ml Erlenmeyer flask containing a magnetic stirring bar wasplaced 20.0 g (5.4 mmoles) of the functionalized molecular includantobtained in Example 15 and 100 g of water. The water was heated to 80°C., at which temperature a clear solution was obtained. To the solutionwas added slowly, with stirring, 3.1 g (6.0 mmoles) of Victoria PureBlue BO (Aldrich). A precipitate formed which was removed from the hotsolution by filtration. The precipitate was washed with 50 ml of waterand dried to give 19.1 g (84 percent) of a blue powder, a coloredcomposition consisting of a mutable colorant, Victoria Pure Blue BO, anda molecular includant having covalently coupled to it an average ofabout six ultraviolet radiation transorber molecules per molecularincludant molecule.

EXAMPLE 19

The procedure of Example 18 was repeated, except that the functionalizedmolecular includant from Example 17 was employed in place of that fromExample 15.

EXAMPLE 20

This example describes mutation or decolorization rates for thecompositions of Examples 7 (wherein the β-cyclodextrin has dehydratedphthaloyl glycine-DAROCUR 2959 from Example 4 covalently bondedthereto), 18 and 19.

In each case, approximately 10 mg of the composition was placed on asteel plate (Q-Panel Company, Cleveland, Ohio). Three drops (about 0.3ml) of acetonitrile (Burdick & Jackson, Muskegon, Mich.) was placed ontop of the composition and the two materials were quickly mixed with aspatula and spread out on the plate as a thin film. Within 5-10 secondsof the addition of the acetonitrile, each plate was exposed to theradiation from a 222-nanometer excimer lamp assembly. The assemblyconsisted of a bank of four cylindrical lamps having a length of about30 cm. The lamps were cooled by circulating water through a centrallylocated or inner tube of the lamp and, as a consequence, they operatedat a relatively low temperature, i.e., about 50° C. The power density atthe lamp's outer surface typically was in the range of from about 4 toabout 20 joules per square meter (J/m²). However, such range in realitymerely reflects the capabilities of current excimer lamp power supplies;in the future, higher power densities may be practical. The distancefrom the lamp to the sample being irradiated was 4.5 cm. The time foreach film to become colorless to the eye was measured. The results aresummarized in Table 6.

                  TABLE 6                                                         ______________________________________                                        Decolorization Times for Various Compositions                                 Composition Decolorization Times (Seconds)                                    ______________________________________                                        Example 18  1                                                                 Example 19  3-4                                                               Example 7   7-8                                                               ______________________________________                                    

While the data in Table 6 demonstrate the clear superiority of thecolored compositions of the present invention, such data were plotted asdegree of substitution versus decolorization time. The plot is shown inFIG. 3. FIG. 3 not only demonstrates the significant improvement of thecolored compositions of the present invention when compared withcompositions having a degree of substitution less than three, but alsoindicates that a degree of substitution of about 6 is about optimum.That is, the figure indicates that little if any improvement indecolorization time would be achieved with degrees of substitutiongreater than about 6.

EXAMPLE 21

This example describes the preparation of a complex consisting of amutable colorant and the derivatized molecular includant of Example 15.

The procedure of Example 18 was repeated, except that the functionalizedmolecular includant of Example 15 was replaced with 10 g (4.8 mmoles) ofthe derivatized molecular includant of Example 15 and the amount ofVictoria Pure Blue BO was reduced to 2.5 g (4.8 mmoles). The yield ofwashed solid was 10.8 g (86 percent) of a mutable colorant associatedwith the β-cyclodextrin having an average of six tosyl groups permolecule of molecular includant.

EXAMPLE 22

This example describes the preparation of a colored composition whichincludes a mutable colorant and a functionalized molecular includant.

The procedure of preparing a functionalized molecular includant ofExample 15 was repeated, except that the tosylated β-cyclodextrin wasreplaced with 10 g (3.8 mmoles) of the complex obtained in Example 21and the amount of the derivatized ultraviolet radiation transorberprepared in Example 15 was 11.6 g (27 mmoles). The amount of coloredcomposition obtained was 11.2 g (56 percent). The average degree ofsubstitution was determined as described above, and was found to be 5.9,or about 6.

EXAMPLE 23

The following two compounds were tested for their ability to stabilizeVictoria Pure Blue BO: ##STR30##

This example further demonstrates the ability of the present inventionto stabilize colorants against light. The two compounds containingVictoria Pure Blue BO as an includant in the cyclodextrin cavity weretested for light fastness under a medium pressure mercury dischargelamp. 100 mg of each compound was dissolved in 20 ml of acetonitrile andwas uniformly spread on steel plates to a thickness of approximately 0.1mm. The plates were then immediately exposed to a medium pressure 1200watt high intensity quartz arc mercury discharge lamp (Conrad-Hanovia,Inc., Newark, N.J.) at a distance of 30 cm from the lamp. The lightfastness results of these compounds are summarized in Table 7.

                  TABLE 7                                                         ______________________________________                                        Cyclodextrin Compound  Fade Time                                              ______________________________________                                        Dehydroxy Compound     >10 min.sup.a                                          Hydroxy Compound       <20 sec                                                ______________________________________                                         .sup.a There is a phase change after 10 minutes due to extreme heat      

EXAMPLE 24

This example describes the preparation of films consisting of colorant,ultraviolet radiation transorber, and thermoplastic polymer. Thecolorant and ultraviolet radiation transorber were ground separately ina mortar. The desired amounts of the ground components were weighed andplaced in an aluminum pan, along with a weighed amount of athermoplastic polymer. The pan was placed on a hot plate set at 150° C.and the mixture in the pan was stirred until molten. A few drops of themolten mixture were poured onto a steel plate and spread into a thinfilm by means of a glass microscope slide. Each steel plate was 3×5inches (7.6 cm×12.7 cm) and was obtained from Q-Panel Company,Cleveland, Ohio. The film on the steel plate was estimated to have athickness of the order of 10-20 micrometers.

In every instance, the colorant was Malachite Green oxalate (AldrichChemical Company, Inc., Milwaukee, Wis.), referred to hereinafter asColorant A for convenience. The ultraviolet radiation transorber("UVRT") consisted of one or more of IRGACURE® 500 ("UVRT A"), IRGACURE®651 ("UVRT B"), and IRGACURE® 907 ("UVRT C"), each of which wasdescribed earlier and is available from Ciba-Geigy Corporation,Hawthorne, N.Y. The polymer was one of the following: anepichlorohydrin-bisphenol A epoxy resin ("Polymer A"), EPON® 1004F(Shell Oil Company, Houston, Tex.); a poly(ethylene glycol) having aweight-average molecular weight of about 8,000 ("Polymer B"), CARBOWAX8000 (Aldrich Chemical Company); and a poly(ethylene glycol) having aweight-average molecular weight of about 4,600 ("Polymer C"), CARBOWAX4600 (Aldrich Chemical Company). A control film was prepared whichconsisted only of colorant and polymer. The compositions of the filmsare summarized in Table 8.

                  TABLE 8                                                         ______________________________________                                        Compositions of Films Containing                                              Colorant and Ultraviolet Radiation Transorber ("UVRT")                        Colorant            UVRT           Polymer                                    Film    Type   Parts    Type Parts   Type Parts                               ______________________________________                                        A       A      1        A    6       A    90                                                          C    4                                                B       A      1        A    12      A    90                                                          C    8                                                C       A      1        A    18      A    90                                                          C    12                                               D       A      1        A    6       A    90                                                          B    4                                                E       A      1        B    30      A    70                                  F       A      1        --   --      A    100                                 G       A      1        A    6       B    90                                                          C    4                                                H       A      1        B    10      C    90                                  ______________________________________                                    

While still on the steel plate, each film was exposed to ultravioletradiation. In each case, the steel plate having the film sample on itssurface was placed on a moving conveyor belt having a variable speedcontrol. Three different ultraviolet radiation sources, or lamps, wereused. Lamp A was a 222-nanometer excimer lamp and Lamp B was a308-nanometer excimer lamp, as already described. Lamp C was a fusionlamp system having a "D" bulb (Fusion Systems Corporation, Rockville,Md.). The excimer lamps were organized in banks of four cylindricallamps having a length of about 30 cm, with the lamps being orientednormal to the direction of motion of the belt. The lamps were cooled bycirculating water through a centrally located or inner tube of the lampand, as a consequence, they operated at a relatively low temperature,i.e., about 50° C. The power density at the lamp's outer surfacetypically is in the range of from about 4 to about 20 joules per squaremeter (J/m²).

However, such range in reality merely reflects the capabilities ofcurrent excimer lamp power supplies; in the future, higher powerdensities may be practical. With Lamps A and B, the distance from thelamp to the film sample was 4.5 cm and the belt was set to move at 20ft/min (0.1 m/sec). With Lamp C, the belt speed was 14 ft/min (0.07m/sec) and the lamp-to-sample distance was 10 cm. The results ofexposing the film samples to ultraviolet radiation are summarized inTable 9. Except for Film F, the table records the number of passes undera lamp which were required in order to render the film colorless. ForFilm F, the table records the number of passes tried, with the film ineach case remaining colored (no change).

                  TABLE 9                                                         ______________________________________                                        Results of Exposing Films Containing                                          Colorant and Ultraviolet Radiation Transorber (UVRT)                          to Ultraviolet Radiation                                                               Excimer Lamp                                                         Film    Lamp A        Lamp B  Fusion Lamp                                     ______________________________________                                        A       3             3       15                                              B       2             3       10                                              C       1             3       10                                              D       1             1       10                                              E       1             1        1                                              F       5             5       10                                              G       3             --      10                                              H       3             --      10                                              ______________________________________                                    

EXAMPLE 25

This Example demonstrates that the 222 nanometer excimer lampsillustrated in FIG. 4 produce uniform intensity readings on a surface ofa substrate 5.5 centimeters from the lamps, at the numbered locations,in an amount sufficient to mutate the colorant in the compositions ofthe present invention which are present on the surface of the substrate.The lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs 20positioned in parallel, the excimer lamp bulbs 20 are approximately 30cm in length. The lamps are cooled by circulating water through acentrally located or inner tube (not shown) and, as a consequence, thelamps are operated at a relatively low temperature, i.e., about 50° C.The power density at the lamp's outer surface typically is in the rangeof from about 4 to about 20 joules per square meter (J/m²).

Table 10 summarizes the intensity readings which were obtained by ameter located on the surface of the substrate. The readings numbered 1,4, 7, and 10 were located approximately 7.0 centimeters from the leftend of the column as shown in FIG. 4. The readings numbered 3, 6, 9, and12 were located approximately 5.5 centimeters from the right end of thecolumn as shown in FIG. 4. The readings numbered 2, 5, 8, and 11 werecentrally located approximately 17.5 centimeters from each end of thecolumn as shown in FIG. 4.

                  TABLE 10                                                        ______________________________________                                        Background (μW)                                                                           Reading (mW/cm.sup.2)                                          ______________________________________                                        24.57          9.63                                                           19.56          9.35                                                           22.67          9.39                                                           19.62          9.33                                                           17.90          9.30                                                           19.60          9.30                                                           21.41          9.32                                                           17.91          9.30                                                           23.49          9.30                                                           19.15          9.36                                                           17.12          9.35                                                           21.44          9.37                                                           ______________________________________                                    

EXAMPLE 26

This Example demonstrates that the 222 nanometer excimer lampsillustrated in FIG. 5 produce uniform intensity readings on a surface ofa substrate 5.5 centimeters from the lamps, at the numbered locations,in an amount sufficient to mutate the colorant in the compositions ofthe present invention which are present on the surface of the substrate.The excimer lamp 10 comprises a lamp housing 15 with four excimer lampbulbs 20 positioned in parallel, the excimer lamp bulbs 20 areapproximately 30 cm in length. The lamps are cooled by circulating waterthrough a centrally located or inner tube (not shown) and, as aconsequence, the lamps are operated at a relatively low temperature,i.e., about 50° C. The power density at the lamp's outer surfacetypically is in the range of from about 4 to about 20 joules per squaremeter (J/m²).

Table 11 summarizes the intensity readings which were obtained by ameter located on the surface of the substrate. The readings numbered 1,4, and 7 were located approximately 7.0 centimeters from the left end ofthe columns as shown in FIG. 5. The readings numbered 3, 6, and 9 werelocated approximately 5.5 centimeters from the right end of the columnsas shown in FIG. 5. The readings numbered 2, 5, 8 were centrally locatedapproximately 17.5 centimeters from each end of the columns as shown inFIG. 5.

                  TABLE 11                                                        ______________________________________                                        Background (μW)                                                                           Reading (mW/cm.sup.2)                                          ______________________________________                                        23.46          9.32                                                           16.12          9.31                                                           17.39          9.32                                                           20.19          9.31                                                           16.45          9.29                                                           20.42          9.31                                                           18.33          9.32                                                           15.50          9.30                                                           20.90          9.34                                                           ______________________________________                                    

EXAMPLE 27

This Example demonstrates the intensity produced by the 222 nanometerexcimer lamps illustrated in FIG. 6, on a surface of a substrate, as afunction of the distance of the surface from the lamps, the intensitybeing sufficient to mutate the colorant in the compositions of thepresent invention which are present on the surface of the substrate. Theexcimer lamp 10 comprises a lamp housing 15 with four excimer lamp bulbs20 positioned in parallel, the excimer lamp bulbs 20 are approximately30 cm in length. The lamps are cooled by circulating water through acentrally located or inner tube (not shown) and, as a consequence, thelamps are operated at a relatively low temperature, i.e., about 50° C.The power density at the lamp's outer surface typically is in the rangeof from about 4 to about 20 joules per square meter (J/m²).

Table 12 summarizes the intensity readings which were obtained by ameter located on the surface of the substrate at position 1 as shown inFIG. 6. Position 1 was centrally located approximately 17 centimetersfrom each end of the column as shown in FIG. 6.

                  TABLE 12                                                        ______________________________________                                                                  Reading                                             Distance (cm) Background (μW)                                                                        (mW/cm.sup.2)                                       ______________________________________                                        5.5           18.85       9.30                                                6.0           15.78       9.32                                                10            18.60       9.32                                                15            20.90       9.38                                                20            21.67       9.48                                                25            19.86       9.69                                                30            22.50       11.14                                               35            26.28       9.10                                                40            24.71       7.58                                                50            26.95       5.20                                                ______________________________________                                    

EXAMPLE 28

This example describes a method of making the followingwavelength-selective sensitizer: ##STR31##

The wavelength-selective sensitizer is synthesized as summarized below:##STR32##

To a 250 ml round bottom flask fitted with a magnetic stir bar, and acondensor, was added 10.8 g (0.27 mole) sodium hydroxide (Aldrich), 98 gwater and 50 g ethanol. The solution was stirred while being cooled toroom temperature in an ice bath. To the stirred solution was added 25.8g (0.21 mole) acetophenone (Aldrich) and then 32.2 g (0.21 mole)4-carboxybenzaldehyde (Aldrich). The reaction mixture was stirred atroom temperature for approximately 8 hours. The reaction mixturetemperature was checked in order to prevent it from exceeding 30° C.Next, dilute HCL was added to bring the mixture to neutral pH. Thewhite/yellow precipitate was filtered using a Buchner funnel to yield40.0 g (75%) after drying on a rotary pump for four hours. The productwas used below without further purification.

The resulting reaction product had the following physical parameters:

Mass. Spec. m/e (m⁺) 252, 207, 179, 157, 105, 77, 51.

EXAMPLE 29

This example describes a method of covalently bonding the compoundproduced in Example 28 to cyclodextrin as is summarized below: ##STR33##

To a 250 ml round bottom flask fitted with a magnetic stir bar,condensor, and while being flushed with argon, was placed 5.0 g (0.019mole) of the composition prepared in Example 29, and 50 ml of anhydrousDMF (Aldrich). To this solution was slowly dropped in 2.5 g (0.019 mole)oxalyl chloride (Aldrich) over thirty minutes with vigorous stirringwhile the reaction flask was cooled in an ice-bath. After one hour, thereaction was allowed to warm to room temperature, and then was stirredfor one hour. The reaction mixture was used "as is" in the followingstep. To the above reaction mixture 5.3 g (0.004 mole) of hydroxyethylsubstituted alpha-cyclodextrin (American Maize Company), dehydrated byDean and Stark over benzene for two hours to remove any water, was addedand the reaction mixture stirred at room temperature with 3 drops oftriethylamine added. After four hours the reaction mixture was pouredinto 500 ml of acetone and the white precipitate filtered using aBuchner Funnel. The white powder was dried on a rotary pump (0.1 mm Hg)for four hours to yield 8.2 g product.

The resulting reaction product had the following physical parameters:

NMR (DMSO-d₆) δ 2.80 M, CD!, 3.6-4.0 M, CD!, 7.9 C, aromatus!,8.2 M,aromatus of C!, 8.3 M, aromatus of C! ppm.

EXAMPLE 30

This example describes a method of making the followingwavelength-selective sensitizer, namely 4- 4'-carboxyphenyl!-3-buten-2-one: ##STR34##

The wavelength-selective sensitizer is synthesized as summarized below:##STR35##

The method of Example 28 was followed except that acetone (Fisher,Optima Grade) was added first, and then the carboxybenzaldehyde wasadded. More particularly, 32.2 (0.21 mole) of carboxybenzaldehyde wasreacted with 12.2 g (0.21 mole) of acetone in the sodiumhydroxide/ethanol/water mixture described in Example 28. Dilute HCl wasadded to bring the reaction mixture to neutral pH, yielding 37.1 g (91%)of a pale yellow powder which was used without further purification inthe following examples.

The resulting reaction product, namely 4- 4'-carboxyphenyl!-3-buten-2-one, had the following physical parameters:

Mass. Spec. 190 (m⁺), 175, 120.

EXAMPLE 31

This example describes a method of covalently bonding the 4- 4'-carboxyphenyl!-3-buten-2-one produced in Example 30 to cyclodextrin as issummarized below: ##STR36##

The method of Example 29 was followed except that 5.0 g of the 4-4'-carboxy phenyl!-3-buten-2-one was used. More particularly, 5.0 g(0.026 mole) of the 4- 4'-carboxy phenyl!-3-buten-2-one produced inExample 30 was reacted with 3.3 g (0.026 mole) of oxalyl chloride inanyhydrous DMF at about 0° C. Next, approximately 7.1 g (0.005 mole)hydroxyethyl substituted cyclodextrin was added to the mixture (5:1ratio) under the conditions described in Example 30 and was furtherprocessed as described therein, to produce 10.8 g of white powder. TheNMR of the product showed both the aromatic protons of the p4-4'-carboxy phenyl!-3-buten-2-one produced in Example 30 and the glucoseprotons of the cyclodextrin.

EXAMPLE 32

This example describes a method of covalently bonding the compoundproduced in Example 28 to a photoreactor, namely DAROCUR 2959, as issummarized below: ##STR37##

To a 500 ml round bottom flask fitted with a magnetic stir bar, andcondensor, was placed 20 g (0.08 mole) of the composition prepared inExample 28, 17.8 g (0.08 mole) DAROCUR 2959 (Ciba-Geigy, N.Y.), 0.5 gp-toluenesulfonic acid (Aldrich), and 300 ml anhydrous benzene(Aldrich). The Dean and Stark adapter was put on the flask and thereaction mixture heated at reflux for 8 hours after which point 1.5 mlof water had been collected (theo. 1.43 ml). The reaction mixture wasthen cooled and the solvent removed on a rotary evaporator to yield 35.4g. The crude product was recrystalized from 30% ethyl acetate in hexaneto yield 34.2 g (94%) of a white powder. The resulting reaction producthad the following physical parameters:

Mass. Spectrum: 458 (m⁺), 440, 399, 322, 284.

EXAMPLE 33

To determine whether the 4- 4'-carboxy phenyl!-3-buten-2-one produced inExample 30 has the capability to stabilize colorants, the followingexperiment was conducted. Test films were made up containing 90%CARBOWAX 4600 and 10% of a 1 part Victoria Pure Blue BO (Aldrich) to 19parts 4- 4'-carboxy phenyl!-3-buten-2-one. The mixture was melted on ahot plate, stirred, then drawn down on metal plates (at approximately60° C.), using a #3 drawdown bar. A similar sample was made with only 1%Victoria Pure Blue BO in 99% carbowax.

The plates were exposed to a 1200 Watt Mercury medium pressure lamp forone hour, the lamp being about 2 feet from the plates. After one hour,the Victoria Pure Blue BO plate was essentially colorless, while theplate having the mixture of Victoria Pure Blue BO and 4- 4'-carboxyphenyl!-3-buten-2-one thereon had not changed.

EXAMPLE 34

A further experiment to determine the colorant stabilizing capability ofthe 4- 4'-carboxy phenyl!-3-buten-2-one produced in Example 30 is asfollows. The experiment used in Example 33 was repeated except that nocarbowax was used. Instead, the materials were dissolved in acetonitrileand a film formed, allowed to dry, and then exposed to the 1200 Wattlamp. Again, after one hour, the dye (Victoria Pure Blue BO) wasessentially colorless while the mixture containing the 4- 4'-carboxyphenyl!-3-buten-2-one was unchanged in color.

EXAMPLE 35

A further experiment to determine the colorant stabilizing capability ofthe compounds produced in Examples 28, 29, 30 (4- 4'-carboxyphenyl!-3-buten-2-one), and 31 (4- 4'-carboxyphenyl!-3-buten-2-one/cyclodextrin) was as follows. The experiment usedin Example 34 was repeated for all four compounds, separately. Moreparticularly, five metal plates were prepared using the acetonitrileslurry method of Example 34, with the compositions as follows:

(1) Victoria Pure Blue BO only;

(2) Victoria Pure Blue BO+the compound produced in Example 28;

(3) Victoria Pure Blue BO+the compound produced in Example 30;

(4) Victoria Pure Blue BO+the compound produced in Example 29;

(5) Victoria Pure Blue BO+the compound produced in Example 31.

In compositions (2) through (5), the compositions contained one partVictoria Pure Blue BO per 20 parts of the compounds produced in theabove examples. More particularly, 0.1 g of Victoria Pure Blue BO wasmixed with approximately 2.0 g of one of the compounds produced in theabove examples, in 10 ml of acetonitrile. The mixtures were drawn downusing a #8 bar and allowed to air dry in a ventilation hood. All of theplates were simultaneously exposed to the 1200 Watt mercury lamp for onehour. Each plate was half covered with aluminum foil during exposure tothe lamp to maintain a reference point with respect to fading of thecolorant. After one hour under the lamp, mixture (1) had gone colorless,while mixtures (2) through (5) all remained unchanged.

EXAMPLE 36

Another experiment to determine the colorant stabilizing capability ofthe compound produced in Example 29 was as follows. Briefly described,the compound of Example 29 was used with color inks removed from thecolor cartridges of a CANON BJC-600e bubble jet color printer. The inkwas reinstalled into the cartridges, which were installed into the inkjet printer, and color test pages were generated. The fortieth colortest page was used in the present study.

More particularly, the four cartridges were of BJI-201, and the fourinks (cyan, magenta, black, and yellow) were prepared as follows:

(1) Cyan

About 3.8 ml of the colored ink in the cartridge was removed, having aviscosity of 12 seconds for 3 ml measured in a 10 ml pipette. About 0.4g of the compound produced in Example 29 was added to the 3.8 ml andmixed for 15 minutes. The ink solution prepared was hazy, and had aviscosity of 19 seconds for 3 ml.

(2) Magenta

About 4.8 ml of the colored ink in the cartridge was removed, having aviscosity of 12 seconds for 3 ml. About 0.43 g of the compound ofExample 29 was added to the 4.8 ml and mixed for fifteen minutes,producing a ink solution having a viscosity of 18 seconds for 3 ml.

(3) Black

About 7.2 ml of the ink in the cartridge was removed, having a viscosityof 8 seconds for 3 ml. About 0.72 g of the compound of Example 29 wasadded to the 7.2 ml and mixed for fifteen minutes, producing a hazy inksolution having a viscosity of 15 seconds for 3 ml.

(4) Yellow

About 4.0 ml of the colored ink in the cartridge was removed, having aviscosity of 4 seconds for 3 ml. About 0.41 g of the compound of Example29 was added to the 4.0 ml and mixed for fifteen minutes, producing ahazy ink solution having a viscosity of 7 seconds for 3 ml.

The cartridges were then refilled with the corresponding ink solutions(1) through (4) above. Forty pages were run off, and the fortieth pagewas exposed to a 1200 Watt medium pressure mercury lamp with a controlsheet for nine hours. The control sheet is the fortieth color test pagerun off using the ink compositions that were in the original inkcartridges.

The results of this experiment were as follows. After three hours underthe 1200 Watt lamp, the control was 40 to 50% bleached, while the inkscontaining the compound produced in Example 29 were unchanged. Afternine hours, the control was 50 to 60% bleached while the inks containingthe compound of Example 29 were only about 10 to 20% bleached.Accordingly, the compound produced in Example 29 is capable ofstabilizing the dyes found in standard ink jet inks.

EXAMPLE 37

Another experiment to determine the colorant stabilizing capability ofthe compound produced in Example 29 is as follows. The stability of theink solutions produced in Example 36 were studied as described below.

The forty-eighth sheet (test sheet) was generated using the inksolutions (1) through (4) of Example 36 each containing about 10% of thecompound of Example 29, and was then exposed to a 1200 Watt lamp alongwith a control sheet (generated from the commercially available ink fromthe cartridges before the compound of Example 29 was added). The sheetswere monitored each hour of exposure and "fade" was determined by theeye against an unexposed sheet. The results of exposing the sheets tothe 1200 Watt lamp are summarized in Table 13, where NC=no change.

                  TABLE 13                                                        ______________________________________                                                     Irradiation                                                      Time (Hour)    Control Sheet                                                                            Test Sheet                                          ______________________________________                                        0              NC         NC                                                  1               5-10%     NC                                                  2              10-15%     NC                                                  3              20%        NC                                                  4              30%        NC                                                  5              50%        NC                                                  ______________________________________                                    

Accordingly, the compound prepared in Example 29 works well as a dyestabilizer to visible and ultraviolet radiation.

Having thus described the invention, numerous changes and modificationshereof will be readily apparent to those having ordinary skill in theart, without departing from the spirit or scope of the invention.

What is claimed is:
 1. A method of light-stabilizing a colorantcomprising associating the colorant with a stabilizing compound selectedfrom the group consisting of 1-Hydroxy-cyclohexyl-phenyl ketone;a,a-dimethoxy-a-hydroxy acetophenone;1-(4-Isopropylphenyl)-2-hydroxy-2-methyl-propan-1-one; 1-4-(2-Hydroxyethoxy)phenyl!-2-hydroxy-2-methyl-propan-1-one; poly2-Hydroxy-2-methyl-1- 4-(1-methylvinyl)phenyl!propan-1-one!;2-Hydroxy-1,2-diphenylethanone; or a mixture thereof, wherein saidcompound has been dehydrated at the position alpha to the carbonylcarbon.
 2. The method of light-stabilizing a colorant of claim 1,wherein the stabilizing compound is associated with a colorant byadmixing, covalent bonding, molecular inclusion, or a combinationthereof.
 3. The method of light-stabilizing a colorant of claim 1,further comprising associating the colorant with a molecular includantselected from the group consisting of a clathrate, an intercalate, azeolite, and a cyclodextrin.
 4. The method of light-stabilizing acolorant of claim 1, wherein the stabilizing compound is covalentlybound to a cyclodextrin.
 5. The method of light-stabilizing a colorantof claim 1, wherein the stabilizing compound is present in solution witha colorant and a cyclodextrin in a concentration of about 0.1% to 50% byweight.
 6. The method of light-stabilizing a colorant of claim 1,wherein the stabilizing compound is present in solution with a colorantand a cyclodextrin in a concentration of about 20% to 30% by weight. 7.A method of light-stabilizing a colorant comprising associating thecolorant with a stabilizing compound represented by the followingformula: ##STR38##
 8. The method of light-stabilizing a colorant ofclaim 7, wherein the stabilizing compound is associated with thecolorant by admixing, covalent bonding, molecular inclusion, or acombination thereof.
 9. The method of light-stabilizing a colorant ofclaim 7, further comprising associating the colorant with a molecularincludant selected from the group consisting of a clathrate, anintercalate, a zeolite, and a cyclodextrin.
 10. The method oflight-stabilizing a colorant of claim 7, wherein the stabilizingcompound is covalently bound to a cyclodextrin.
 11. A method oflight-stabilizing a colorant comprising associating the colorant with astabilizing compound represented by the following formula: ##STR39## 12.The method of light-stabilizing a colorant of claim 11, wherein thestabilizing compound is associated with a colorant by admixing, covalentbonding, molecular inclusion, or a combination thereof.
 13. The methodof light-stabilizing a colorant of claim 11, further comprisingassociating the colorant with a molecular includant selected from thegroup consisting of a clathrate, an intercalate, a zeolite, and acyclodextrin.
 14. The method of light-stabilizing a colorant of claim11, wherein the stabilizing compound is covalently bound to acyclodextrin.
 15. A method of light-stabilizing a colorant comprisingassociating the colorant with a stabilizing compound represented by thefollowing formula: ##STR40##
 16. The method of light-stabilizing acolorant of claim 15, wherein the stabilizing compound is associatedwith the colorant by admixing, covalent bonding, molecular inclusion, ora combination thereof.
 17. The method of light-stabilizing a colorant ofclaim 15, further comprising associating the colorant with a molecularincludant selected from the group consisting of a clathrate, anintercalate, a zeolite, and a cyclodextrin.
 18. The method oflight-stabilizing a colorant of claim 15, wherein the stabilizingcompound is covalently bound to a cyclodextrin.